Heavy REE Depletion Research Articles

Trace element geochemistry of nyerereite and gregoryite phenocrysts from natrocarbonatite lava, Oldoinyo Lengai, Tanzania: Implications for magma mixing

The abundances of Li, P, Cl, V, Mn, Rb, Sr, Y, Cs, Ba, Pb, Th, U and REE, within and between, phenocrysts of nyerereite and gregoryite occurring in natrocarbonatite lavas erupted from the active volcano Oldoinyo Lengai (Tanzania) have been determined by electron microprobe, LA-ICP-MS and SIMS. These data show that, in general, nyerereite is enriched in Rb (71–137ppm), Sr (14,485–23,240ppm), Y (2.0–8.9ppm), Cs (1.6–5.3ppm), Ba (4000–11,510ppm), but poorer in Li (21–91ppm), P (820–1900ppm) and V (5.1–47ppm) relative to gregoryite (Rb=43–106; Sr=4255–7275; Y=0.3–4.0; Cs=0.6–5.1; Ba=1125–7052; Li 84–489; P=6790–15,860; V=33–155ppm). Nyerereite is highly enriched in REE (La=236–973; Ce=395–1044ppm) relative to gregoryite (La=59–309; Ce=59–301ppm). Chondrite normalized REE distribution patterns for nyerereite and gregoryite are parallel and linear with no Eu anomalies. They show extreme enrichment in light REE and depletion in heavy REE (nyerereite La/YbCN=1759–7079; gregoryite La/YbCN=1051–10,247). Significant differences exist in the abundances of trace elements within and between coexisting crystals occurring in diverse natrocarbonatite flows, although there do not appear to be any significant secular variations in phenocryst compositions in lavas erupted from a given vent. It is concluded that both major, minor and trace element compositional data for nyerereite and gregoryite phenocrysts occurring in natrocarbonatite lavas are derived by the crystallization of several different batches of magma in a continuously replenished fractionating magma chamber. Natrocarbonatite lavas are considered to be hybrids formed by the mixing of both crystals and melts formed from several batches of natrocarbonatite magma; thus bulk rock compositions cannot represent the compositions of the primary magma composition before the onset of fractionation. Differentiation of natrocarbonatite melts leads to enrichment of residua in Ba and Mg.

Lithogeochemistry as a tracer of the tectonic setting, lateral integrity and mineralization of a highly metamorphosed Mesoproterozoic volcanic arc sequence on the eastern margin of the Namaqua Province, South Africa

The Areachap Group represents the medium- to high-grade metamorphic and deformed remnants of a Mesoproterozoic (ca. 1.24–1.30 Ga) volcanic arc that was accreted onto the western margin of the Kaapvaal Craton during the early stages of the Namaqua-Natal Orogeny. Few regional geochemical studies of the succession have been undertaken and despite recent geochronological work from throughout the outcrop belt there is still uncertainty as to the lateral integrity and correlation of the succession from one area to another. This uncertainty has been aided by minimal outcrop and extensive deformation and dislocation of one area from another. This study uses trace element geochemistry combined with Sm–Nd-isotopic data from the northern and southern ends of the succession to test its lateral integrity. Minor differences, including the abundance of certain lithologies, varying influences of a crustal component and differences in age between different areas are apparent, but the succession, as a whole, displays lateral integrity as a continental island arc. All lithologies are characterised by enrichment in Th, U, Pb and the large ion lithophile elements relative to primitive mantle, along with Nb–Ta depletion relative to La, and strong light rare earth element (LREE) enrichment relative to heavy REE depletion, which, along with positive ε Nd(t) values of mafic gneisses from both ends of the succession, indicates mantle-derivation within a subduction-related environment with a substantial amount of crustal assimilation. Despite some minor geochemical and isotopic differences in the lithological architecture on a local scale the Areachap Group exhibits coherent geochemical characteristics along its entire strike length. Localised remobilization of elements, particularly in areas characterised by granulite grade metamorphism, as well as in the altered footwall zones of volcanogenic massive sulphide lenses, is present. These alteration trends, along with primary geochemical signatures are remarkably well preserved despite the high grade of metamorphism, as illustrated in clearly defined hydrothermal alteration trends on the alteration box plot, and serves as an efficient tool to delineate areas that have undergone hydrothermal alteration spatially associated with massive sulphide ore bodies. The systematic association of hydrothermal alteration and sulphide ore bodies provides support for the isochemical character of rock compositions during high-grade metamorphism and the lack of extensive post-metamorphic alteration processes.

Using in situ REE analysis to study the origin and diagenesis of dolomite of Lower Paleozoic, Tarim Basin

In situ REE concentrations of various dolomites from Tarim Basin were obtained by LA-ICP-MS analysis, and the data were normalized to standard seawater (Seawater Normalized=SWN). Most of the samples have a ΣREE range of less than 20 ppm. All samples show similar REESWN distributions with heavy REE depletion, and positive Ce anomaly, which indicates that they have the same dolomitization fluids (seawater). According to the origin and diagenetic process of dolomite, two types of dolomite are determined and described as follows: 1) syndepositional dolomite, with the highest REE concentrations (more than 20 ppm), the cores of which are more enriched in REE compared with their cortexes, indicating that they underwent the dolomitization of calcareous sediments by hypersaline and subsequent diagenesis decreased the REE content of the cortex because of the low REE concentration of the diagenetic fluids; 2) diagenetic dolomite, which can be subdivided into four groups. (1) burial dolomite which has higher REE concentrations than limestone, but lower than syndepositional dolomite. This shows that pore fluids with high salinity dolomitized the pre-existing limestone; (2) void filling dolomite which has the similar REE patterns with the matrix dolomite. In addition, the Eu anomaly is not obvious, suggesting that the dolomitization fluids originated from the diagenetic fluids; (3) recrystallized dolomite, whose REE concentration was obviously decreased, indicating that the REE concentration was decreased during the recrystallization processes; and (4) hydrothermal altered void-filling dolomite, which has the lowest REE concentration, but obvious positive Eu anomaly, reflecting its hydrothermal activity related origin. Thus, the diverse REE signatures, which were recorded in different dolomites, retain the information of their formation conditions and subsequent diagenetic processes. In situ REE analysis of dolomite is an effective probe into the origin and diagenetic process of dolomite.

Petrology of chloritoid–ilmenite-rich rocks in the Indus Suture mélange of Pakistan: Implications for the Cretaceous paleolatitude of Kohistan

The Indian Plate and Kohistan Island Arc are juxtaposed to the north of Peshawar along the Indus Suture, which is characterized by a tectonic mélange consisting of ultramafic, mafic, and a variety of sedimentary rocks. Within metavolcanic greenstones, there are small, lensoid bodies comprising quartz, white mica (up to 4.5 wt% FeO), chlorite (pseudothuringite to ripidolite), pyrite, and abundant chloritoid (up to 60%) and ilmenite. These lenses consist essentially of SiO 2, TiO 2, Al 2O 3 and iron oxide. There is a clear petrographic and geochemical (major, trace and RE element) transition from these rocks to their host greenstones, suggesting a common parentage. The greenstones contain high TiO 2, Fe 2O 3 and P 2O 5. Their chondrite-normalized patterns show enrichment in light REE, depletion in heavy REE, negative Eu and positive Yb anomalies. Because the greenstones have probably been altered, the present set of data is not capable of deciphering the tectonic setting of these rocks, but previous geochemical studies have suggested an island arc setting for volcanic rocks in the mélange. By chemical analogy with lateritized basalts, the chloritoid-rich rocks are considered to be the product of weathering of basalts in tropical, probably equatorial, conditions before the northward drift of Kohistan. Mélange formation and greenschist facies metamorphism occurred during the collision of the Indian Plate and the Kohistan Magmatic Arc, to its north, in the Late Cretaceous-Early Tertiary.

Petrogenesis of Cretaceous adakitic and shoshonitic igneous rocks in the Luzong area, Anhui Province (eastern China): Implications for geodynamics and Cu–Au mineralization

Both adakitic and shoshonitic igneous rocks in the Luzong area, Anhui Province, eastern China are associated with Cretaceous Cu–Au mineralization. The Shaxi quartz diorite porphyrites exhibit adakite-like geochemical features, such as light rare earth element (LREE) enrichment, heavy REE (HREE) depletion, high Al 2O 3, MgO, Sr, Sr / Y and La / Yb values, and low Y and Yb contents. They have low ε Nd( t) values (− 3.46 to − 6.28) and high ( 87Sr / 86Sr) i ratios (0.7051–0.7057). Sensitive High-Resolution Ion Microprobe (SHRIMP) zircon analyses indicate a crystallization age of 136 ± 3 Ma for the adakitic rocks. Most volcanic rocks and the majority of monzonites and syenites in the Luzong area are K-rich (or shoshonitic) and were also produced during the Cretaceous (140–125 Ma). They are enriched in LREE and large-ion lithophile elements, and depleted in Ti, and Nb and Ba and exhibit relatively lower ε Nd( t) values ranging from − 4.65 to − 7.03 and relatively higher ( 87Sr / 86Sr) i ratios varying between 0.7057 and 0.7062. The shoshonitic and adakitic rocks in the Luzong area have similar Pb isotopic compositions ( 206Pb / 204Pb = 17.90–18.83, 207Pb / 204Pb = 15.45–15.62 and 208Pb / 204Pb = 38.07–38.80). Geological data from the Luzong area suggest that the Cretaceous igneous rocks are distributed along NE fault zones (e.g., Tanlu and Yangtze River fault zones) in eastern China and were likely formed in an extensional setting within the Yangtze Block. The Shaxi adakitic rocks were probably derived by the partial melting of delaminated lower crust at pressures equivalent to crustal thickness of > 50 km (i.e., ∼1.5 GPa), possibly leaving rutile-bearing eclogitic residue. The shoshonitic magmas, in contrast, originated mainly from an enriched mantle metasomatized by subducted oceanic sediments. They underwent early high-pressure (> 1.5 GPa) fractional crystallization at the boundary between thickened (> 50 km) lower crust and lithospheric mantle and late low-pressure (< 1.5 GPa) fractional crystallization in the shallow (< 50 km) crust. The adakitic and shoshonitic rocks appear to be linked to an intra-continental extensional setting where partial melting of enriched mantle and delaminated lower crust was probably controlled by lithospheric thinning and upwelling of hot asthenosphere along NE fault zones (e.g., Tanlu and Yangtze River fault zones) in eastern China. Both the shoshonitic and adakitic magmas were fertile with respect to Cu–Au mineralization.

Effects of Hydrothermal Alteration on Geochemical Characteristics of the El Sukkari Granite, Central Eastern Desert, Egypt

The El Sukkari granite is predominantly peraluminous and classified as intrusive in a syn-collisional setting. Geochemical evidence suggests that this granite was generated by partial melting of metagraywackes at ˜800°C as deduced from zircon saturation temperatures. The El Sukkari granite underwent multistage hydrothermal processes accompanying gold mineralization. Intensive hydrothermal alteration of the granite occurred along brittle structures that are mostly filled by dikes and quartz veins. Sodic and potassic metasomatism are the major alteration effects. Hydrothermal alteration is indicated by depletion of both light and heavy REE and Eu-enrichment. Eu-enrichment is due largely to chemical contribution from hydrothermal fluids. Other major and trace elements were enriched or depleted during one of the main alteration stages. Rb, Zn, Nb, Zr, T, Y, and Ga show depletion. Ba and Sr display enrichments, whereas Co, Li, and Cr underwent insignificant changes. Ground gamma-ray spectrometry measurements indicate that radioactive element concentrations are generally low in the altered granite. Correlations between eU, eTh, and eU/eTh of the altered granite and the plot of chemically measured U against corresponding Th values for both fresh and altered granites reflect the geochemical coherence of uranium and thorium during magma crystallization. Both elements are mainly hosted in accessory phases and were not disturbed by the hydrothermal alteration.

TTGs and adakites: are they both slab melts?

Although both high-Al TTG (tonalite–trondhjemite–granodiorite) and adakite show strongly fractionated REE and incompatible element patterns, TTGs have lower Sr, Mg, Ni, Cr, and Nb/Ta than most adakites. These compositional differences cannot be easily related by shallow fractional crystallization. While adakites are probably slab melts, TTGs may be produced by partial melting of hydrous mafic rocks in the lower crust in arc systems or in the Archean, perhaps in the root zones of oceanic plateaus. It is important to emphasize that geochemical data can be used to help constrain tectonic settings, but it cannot be used alone to reconstruct ancient tectonic settings. Depletion in heavy REE and low Nb/Ta ratios in high-Al TTGs require both garnet and low-Mg amphibole in the restite, whereas moderate to high Sr values allow little, if any, plagioclase in the restite. To meet these requirements requires melting in the hornblende eclogite stability field between 40- and 80-km deep and between 700 and 800 °C. Some high-Al TTGs produced at 2.7 Ga and perhaps again at about 1.9 Ga show unusually high La/Yb, Sr, Cr, and Ni. These TTGs may reflect catastrophic mantle overturn events at 2.7 and 1.9 Ga, during which a large number of mantle plumes bombarded the base of the lithosphere, producing thick oceanic plateaus that partially melted at depth.

Geochemistry of late Archaean stromatolites from Zimbabwe: evidence for microbial life in restricted epicontinental seas

We report comprehensive trace element and Sr-isotope data for microbial carbonates from the Archaean Mushandike limestone, Masvingo Greenstone Belt, Zimbabwe. The stromatolites have very coherent REE+Y patterns and share the essential shale-normalised characteristics of other Archaean marine precipitates (positive La and Gd anomalies, absence of a negative Ce anomaly and a strongly superchondritic Y/Ho ratio). Mixing models constrain the maximum amount of shale contamination to 0.25–1% and calculated detritus-free carbonate REE+Y systematics require precipitation from seawater. In terms of light-REE over heavy-REE depletion, however, the studied samples are very different from all other known Archaean marine precipitates. In shale-normalised plots, the Mushandike samples yield a negative slope. A very restricted, regional input source of the dissolved load is indicated because normalisation with locally occurring tonalite gneiss REE+Y data yields a pattern closely resembling typical shale-normalised Archaean marine chemical sediments. The disappearance of a negative Eu anomaly when patterns are normalised with local tonalite gneiss strengthens this interpretation. Sr-isotope ratios are strongly correlated with trace element contents and ratios, which explains the modest scatter in Sr-isotope ratios as representing (minor) clastic contamination. Importantly, even the least contaminated samples have very radiogenic initial 87 Sr/ 86 Sr ratios (0.7184) implying Sr input from an ancient high Rb/Sr source, such as the early Archaean gneisses of south-central Zimbabwe. A local ancient (3.5–3.8 Ga) source is also indicated by previously published Pb-isotope datasets for the Mushandike stromatolites. This is entirely compatible with the occurrence of 3.7–3.8 Ga zircons in quartzites and metapelites from comparably old greenstone belts within less than 150 km of the studied locality. Comparison of the Pb-isotope ratios of the Mushandike stromatolites with 2.7 and 2.6 Ga old stromatolites from the neighbouring Belingwe Greenstone Belt demonstrates differences in initial isotope composition that relate to the extent of exchange with the open ocean. The development of numerous basins on old continental crust, with water masses variably restricted from the open ocean, suggests a lack of strong vertical topography on this late Archaean craton.

Dating high-grade metamorphism—constraints from rare-earth elements in zircon and garnet

We integrate petrography and SIMS REE analyses of garnet and polyphase zircon from a pelitic granulite adjacent to the Ronda peridotite, Betic Cordillera, southern Spain to constrain the significance of zircon U–Pb geochronology. Sillimanite inclusions in garnet rims suggest that they grew during decompression, and Ca enrichment in their rims records initiation of partial melting. Chondrite-normalised REE profiles of zircon cores are typically magmatic (positive La to Lu slope and Ce anomaly), whereas overgrowths have flat or negatively sloping heavy-REE profiles (Gd–Lu). The presence of rimmed zircon grains only in the garnet rims and the matrix suggests that this zircon phase grew after garnet had already sequestered heavy REEs, a process documented here by progressive depletion of heavy REE in the garnets from centre to rim. Combined with the textural evidence, we suggest that the U–Pb age of 21.3±0.3 Ma obtained from the zircon rims dates a point on this decompression path rather than the peak metamorphic pressure.

Rare earth elements in zircon: a review of applications and case studies from the Outer Hebridean Lewisian Complex, NW Scotland

Abstract Rare earth element (REE) analysis of zircon coupled with high spatial resolution U-Pb geochronology and imaging is emerging as a useful petrogenetic tool capable of providing a link between dated zircon growth and contemporaneous magmatic conditions or metamorphic reactions. Notable amongst recent studies has been the link established between zircon growth in equilibrium with garnet and characteristic heavy REE depletion in zircon which has enabled the dating of specific pressure-temperature (P-T) evolution. Links to other REE-bearing minerals have yet to be established but have similar potential for dating P-T pathways. A brief review of recent applications in both igneous and metamorphic zircons is presented here to illustrate the range of investigations in this rapidly developing area. The method is then applied to two case studies from the late-Archaean Lewisian Composite Terrane of the Outer Hebrides, NW Scotland. In both cases, these new zircon REE analyses reveal previously unknown events in the early history of these samples, as well as clarifying the relationship of different zircon growth phases in relation to the geochronology.

Slab melting as an explanation of Quaternary volcanism and aseismicity in southwest Japan

Two volcanoes on the Quaternary volcanic front in southwest Japan have erupted medium-K andesite and dacite, which are chemically similar to adakites (i.e., high Al 2 O 3 , Sr/Y, low Y, and steep rare earth element [REE] patterns with no negative Eu anomalies), unlike other subduction-related volcanoes in Japan. Earthquake data and the extrapolated position of the Philippine Sea plate from its near-trench position indicate that the leading edge of the plate is ∼75–100 km deep beneath these volcanoes. Melting of the plate at this depth would leave a garnet eclogite residual, accounting for the Y and heavy REE depletion. The lack of seismic data and active volcanism in southwest Japan can be attributed to the attenuated seismic response of the plate due to melting and to the atypical nature of magma generation.

Geochemistry of the nain massif anorthosite, labrador: Magma diversity in five intrusions

The petrography and major- and trace-element concentrations of the anorthositic Bird Lake Massif (BLM), Susie Brook Slab (SBS), Lister Massif (LM), Port Man vers Run (PMR), and Kikkertavak area (KIK) in the Nain Plutonic Suite (NPS), Labrador, delineate the mineralogical and composition ranges of these large intrusions. From these, a variety of magmas and staging histories can be inferred. The BLM and SBS are mainly noritic anorthosites of the western region exposed along Tikkoatokhakh Bay (TIK). Tilting and stretching deformation distinguish SBS from BLM, but the two units show no mineralogical or chemical differences. The KIK and PMR intrusions are mainly troctolitic to noritic anorthosites of the eastern region, and they contain more mafic components than the TIK bodies. Chemically, all the anorthositic rocks are high in Ba, Sr, and the ratio K Rb , and low in Zr, Rb, and Rb Sr . The three plutonic bodies, BLM, SBS, and LM, along TIK are similar and can be clearly distinguished from KIK and PMR intrusions by element concentrations and ratios. Diagrams of element pairs show that each intrusion or group has its own evolutionary trend and variable style, indicating that they represent independent magma batches rather than fractionally related volumes of the same magma. REE patterns show light REE enrichment and heavy REE depletion, and strong positive Eu anomalies, correlated with cumulus plagioclase. In chemical comparison with adjacent plutons, one PMR-chilled leucotroctolite, after subtraction of 18% cumulus plagioclase, is similar to the Kiglapait magma (KI); one melatroctolite in KIK is close to the comb-layered melatroctolite of the Snowflake zone in the Hettasch Intrusion (HI); and the average leucotroctolite and leuconorite in KIK are similar to the leucotroctolite unit and the upper leuconorite, respectively, at Paul Island (PI). Therefore, the magmas from PMR and KIK are similar to those of wellknown troctolitic bodies and their feldspar-rich cumulates. KIK differs from PMR in having somewhat higher An and Xmg values. All these lines of evidence show that at least three types of magma existed in the study area: sodic noritic magma accumulating plagioclase in TIK, troctolitic magma in KIK, and a magma similar to but more evolved than KIK in PMR. The methods used also illustrate the feasibility of characterizing magma compositions from diverse types of cumulates. Regional differences in modal and chemical composition occur in the NPS. Noritic compositions with pale plagioclase are located in the western and southern regions, and troctolitic compositions with darker plagioclase are located in the eastern region. A reasonably accurate boundary can now be drawn between the two regions, which differ in the nature of their transport from the mantle. In comparison with a primitive mantle composition, high Ba, Pb, K, Sr, Ti, and low Rb, Nb, Zr in the Nain anorthositic rocks are distinctive. These anomalies and the isotopic results of other investigators are consistent with mantle source enrichment followed by variable contamination during magma ponding at the base of the depleted crust.

High field strength and transition element systematics in island arc and back-arc basin basalts: Evidence for multi-phase melt extraction and a depleted mantle wedge

The geochemical character of the mantle wedge in convergent margin settings is investigated using the high field strength and transition elements Ti, Zr, V, Sc and Y in basaltic rocks from island arcs and associated back-arc basins. Systematic differences are observed in the composition of each arc relative to the adjacent back-arc basin. The arcs have lower average abundances of incompatible high field strength elements and Y, and extend to higher ratios of Ti/Zr, V/Ti and Sc/Y. Partial melting of a normal mid-ocean ridge basalt source accounts for the back-arc basin basalt compositions, but cannot explain the higher element ratios observed in many arc basalts. These arc magmas are consistent with derivation from sources which are more depleted in incompatible elements those that of the back-arc basin basalts. Source depletion by melt extraction, prior to arc magma genesis, explains the similar degree of Y depletion and, by analogy, the heavy REE depletion, to that of the high field strength elements in island arc basalts. The observations are not compatible with the presence of residual titanate phases (e.g. rutile). However, amphibole may be required in the source of a subgroup of arc basalts which have relatively high Zr abundances and anomalously low Ti/Zr and high V/Ti values. These results have implications for subduction zone geochemical budgets, as the influence of any slab-derived component may be enhanced in regions of extensive mantle wedge depletion.

Experimental melting of hydrous low-K tholeiite: evidence on. the origin of Archaean era tons

Experimental melting studies were performed on a natural high-Al basalt and a synthetic average Archaean tholeiite (AAT) composition (0.3 wt.% K20) with variable amounts of H20. Microprobe analyses of quenched melts (glass) from runs at 5-30 kbar and 750°-l100°C showed that typical Archaean tonalitic and trondhjemitic "grey gneiss" compositions were produced from the average Archaean tholei-ite over the entire experimental range, with 15% to less than 1 % H20. The high-Al basalt produced liquids too high in Al203 (18--23%) for realistic grey gneiss compositions. The persistent generation in our experiments of low-K calc-alkaline magmas directly by vapor-undersaturated partial melting of low-K Archaean tholeiite strongly suggests this mechanism for the origin of early continents. Temperatures of 850°-l000°C and pressures around 15 kbar are appropriate melting conditions. Ton­alitic magmas are favored by higher temperatures, lower pressures, and higher H20 contents in the source. Trondhjemitic magmas are favored by lower temperatures, higher pressures, and lower H20 contents. Heavy REE depletion of magmas would be possible for partial melting above 15 kbar because of the stability at higher pressures of residual garnet. Unfractionated REE patterns of magmas could result from melting at lower pressures, where garnet does not coexist with liquid. The low-K trends of melts are maintained by very refractory amphibole (up to 0.7 wt. % KzO) which coexists with liquid for bulk H20 contents of 2 wt. % or more. Shallow subduction-zone melting of amphibolite with magma extraction, and partial melting of amphibolite under deep-crustal metamorphic conditions are models for early crustal evolution which appear to satisfy the experimental constraints.

Chemical composition of Archaean komatiites: Implications for early history of the earth and mantle evolution

Estimates of the chemical composition of the Archaean mantle, derived from elemental abundance ratios in komatiites combined with ultramafic xenolith data, support a model of a multistage heterogeneous accretion history of the Earth and synchronous core formation, 4.6 Ga ago. Most refractory lithophile element abundance ratios in komatiites and xenoliths are close to chondritic except for V/Ti and Ca/Al. Depletion of vanadium is likely due to its partial incorporation into the iron core; whereas fractionation of Ca/Al observed in Archaean Al-undepleted komatiites (1.20 times chondrites) and in some modern fertile spinel lherzolite xenoliths (1.15 times chondrites) could be due to small amounts of garnet (rich in Al but poor in Ca) segregation into the lower mantle during partial or complete melting of the upper mantle in the very early history of the Earth. However, this process may have had only a small effect on the overall chemical composition of the upper mantle. Simultaneous occurrence of early Archaean Al-undepleted (Al/Ti ∼ chondrites) and Al-depleted (Al/Ti ∼ 0.5 chondrites, and depletion of Sc and heavy REE) peridotitic komatiites in the Barberton area, S. Africa, and late Archaean Newton Township, Canada, argue against derivation of peridotitic komatiites from a circum-global magma ocean. Garnet separation from a mantle diapir which intersects the solidus at great depth (⩾ 200 km) in a hotter early Archaean mantle could explain the chemical characteristics of Al-depleted komatiites. Alternatively, these two types of komatiites could have been derived from different layers in a fractionated mantle. A limited amount of Hf isotope data for Archaean komatiites seems to suggest that both mechanisms are important. This chemically and minerallogically layered mantle, if it existed, was homogenized by mantle convection after early Archaean times. Constant P 2O 5/TiO 2, Ni/Mg, Co/Mg, Fe/Mg ratios (siderophile/lithophile) and PGE abundances, estimated for the mantle sources of komatiites from Archaean to modern times, strongly argue against continuous growth of the Earth's core since the early Archaean. Extensive crustal contamination might have been involved in the generation of Archaean-early Proterozoic siliceous high magnesian basalts with “boninite affinity”. However, involvement of chemically modified ancient continental lithosphere may also be important in the generation of these basalts.

Rare earth element geochemistry of Central Pacific ferromanganese encrustations

Analyses have been made of the REE contents of a suite of hydrogenous δMnO 2-rich ferromanganese encrustations obtained from a variety of depths (1000–4700 m) on the Line Islands Archipelago. The crusts form a coherent sample group, the REE contents of which are distinctly higher than those of diagenetic nodules. Crusts from 1 to 2 km depth exhibit higher Mn/Fe ratios and are approximately 50% REE depleted with respect to crusts below ∼ 2 km. Furthermore, the shale-normalised patterns of the REE fall into the same depth-related categories. Crusts from depths greater than 2000–2500 m exhibit slight heavy REE depletion relative to intermediate REE whilst crusts from above that level exhibit more fractionated, heavy-REE-enriched patterns. To explain these depth-related processes, it is proposed that Mn and Fe oxides exhibit distinct behaviour with respect to REE scavenging. Between ∼ 1 and 2 km, higher Mn/Fe ratios in the crusts are considered to be caused by an enhanced supply of Mn 2+ —by diffusion and advection from nearshore sediments—which is adsorbed by and occludes existing oxide flocs. At these depths, oxides therefore tend to exhibit predominantly Mn oxide adsorptive properties. Consideration of the REE patterns shows that Fe oxides must be enriched overall in REE relative to Mn oxides and exhibit a flat shale-normalised REE pattern, whilst Mn oxide exhibits a heavy-REE-enriched pattern. Comparison of dissolved REE depth profiles with the crust data enables a qualitative appraisal of the application of scavenging models to the oxide-REE system. The data are not simply described by either equilibrium or irreversible adsorption models alone. It is concluded that whilst oxides may play a general role in creating the LREE depleted seawater pattern, they have little effect on individual vertical profiles, except close to points where fresh oxides precipitate.

Petrogenesis of Archean granitoid plutons from the Kenora area, English River Subprovince, Northwest Ontario, Canada

In the Kenora area, the emplacement of granitoid plutons and associated minor intrusions into older tonalitic gneiss and remnant mafic supracrustal rocks, represents the second half of a protracted history during the Kenoran Orogeny. The oldest granitoid pluton is the Marginal granodiorite (2735 ± 65 Ma) which separates gneiss of the English River Subprovince from supracrustal rocks of the Wabigoon Subprovince. This unit has a narrow, elongate form and a gradational boundary with the gneiss. These features, and the unit's age, initial Sr ratio and REE patterns that are analytically indistinguishable from those of the tonalitic gneiss, are reasons for interpreting the Marginal granodiorite as being derived by ‘frictional reconstitution’ of tonalitic gneiss, resulting from heating during movement along the Kenora fault. The Melick tonalite (2630 ± 50 Ma), and the Lulu and Dalles granodiorites (2630 ± 10 Ma) are interpreted as the next additions to the area. A correlation between decreasing age, increasing initial Sr ratio, increasing size of intrusive body, and progressive depletion of heavy REE may indicate that the Kenora tonalitic gneiss, Melick tonalite, Lulu granodiorite and Dalles granodiorite represent a continuum of genetically related plutonism. The changes in heavy REE suggest that progressively younger source rocks (all comparable to Archean tholeiite) underwent transformation from high-pressure granulite to eclogite. The Dalles granite is modelled by fractional crystallization of the Dalles granodiorite. The youngest plutons are the Muriel diorite-granodiorite (2660 ± 25 Ma) and the Austin granite (2631 ± 63 Ma), both interpreted as being derived from upper crustal rocks. A sequence of dioritic rocks occupies an intermediate structural and lithological position between the amphibolite-tonalite gneiss and the Muriel granodiorite. The model advanced is that the diorites represent the ‘roots’ of major diorite plutons, and indicate derivation by partial melting of amphibolite (and perhaps also low pressure granulite) and tonalitic gneiss. The melt, and some residual material, was mobilized upward along structurally controlled paths. The Austin granite is a potassic pluton with a higher initial Sr ratio than other units in the area. It is interpreted as being derived by extensive partial melting of rocks comparable to the Lulu or Dalles granodiorite.

Trace element mobility in the mylonite zone within the ophiolite aureole, St. Anthony Complex, Newfoundland

The late syntectonic mylonite zone (45–100 m thick) within the dynamothermal aureole of the St. Anthony Complex in northwestern Newfoundland was derived from surrounding quartz and epidote amphibolites by deformation and the nearly isovolumetric metasomatism. Amphibolites have a composition typical of light REE-depleted ocean-floor tholeiites. Mylonites (biotite amphibolites) resemble transitional alkali basalts in major and trace element composition and in the interrelation among relatively immobile elements such as Ti, Zr, Nb, Y and P. Their REE patterns are enriched in light REE and show gradual depletion of heavy REE with La/Yb ratios ranging from 8.4 to 18.4. The results emphasize the need for caution in interpreting the concentration and ratios of any elements in mafic rocks which have been affected by metasomatism in an amphibolite facies shear zone.

Rare earth distribution in Archean granitoid plutons of the Wabigoon volcanic–plutonic belt, northwestern Ontario

Rare earths (La to Lu, Y) are investigated for five Archean granitoid stocks of Kenoran age that intrude the Wabigoon volcanic–plutonic belt. Homogeneous granodiorites are characterized by low total rare earth concentrations (ΣREE), with chondrite-normalized REE patterns that show steep negative slopes, no Eu anomalies, and enrichment of Lu. A hypabyssal porphyry of possible volcanic affiliation displays similar REE patterns, but is more depleted in heavy REE. Zone plutons yield patterns of steep slope, no Eu anomalies, with or without Lu enrichment. REE concentrations decrease from monzodioritic margins, to granodioritic cores, to aplitic apophyses.These plutons carry REE concentrations similar to the Canadian Shield average, but notably lower than some published averages for granitoids. No secular change is evident for the Archean interval.ΣREE decreases during differentiation with no appreciable fractionation of heavy over light REE, until the end stages. Late differentiates suffer depletion in heavy REE by hornblende fractionation. Lu enrichment correlates with deuteric metasomatism, as evidenced by microcline megacrysts. Eu anomalies are absent because fractionation of divalent Eu is prevented by high concentrations of Sr and Ba.Quantitative source modeling should consider the complete magma history of emplacement, crystallization, and deuteric metasomatism.

REE distributions in a high-grade Archaean gneiss complex in Scotland: Implications for the genesis of ancient sialic crust

Seventeen rocks from the Lewisian Gneiss of the Inner Hebrides of Scotland, which represent three distinct lithological types at granulite to greenschist facies of metamorphism show rare-earth element patterns which seem not to have been disturbed by their complex metamorphic history. Some indication of their origin can be obtained by simple geochemical models. Three tonalitic pyroxene gneisses are characterized by: (1) light REE enrichment and heavy REE depletion; (2) low total REE contents; (3) moderate Eu enrichment. Their REE chemistry can be approximated by a model involving 10% partial melting of various garnet-bearing basaltic source materials. Alternatively, they may be some form of crystal cumulate, preserving their original anhydrous mineralogy, representing 30% crystallization of a parent tonalitic magma. Three tonalitic to granodioritic hornblende-biotite gneisses are characterized by: (1) light REE enrichment and heavy REE depletion; (2) significantly higher total REE contents than the pyroxene gneisses; (3) moderate Eu depletion. Their REE patterns can be approximated by a residual silicic melt in a model involving 30% fractional crystallization of solids with the modal mineralogy of the pyroxene gneisses or 40% removal of pure anorthosite from a parent dacitic magma. Two strongly metasomatised diopside-actinolite gneisses and one highly sheared epidote-chlorite gneiss have REE patterns which are not significantly different from the hornblende-biotite gneisses which were their precursors before metasomatism and late greenschist-facies shearing. This suggests that strong alteration has not enciphered the REE systematics of the gneisses. Basic gneisses of quartz tholeiite composition occurring as early dykes, which shared the same metamorphic history as the tonalitic to granodioritic gneisses, are characterised by: (1) slight enrichment in light REE relative to heavy REE; (2) variable total REE contents; (3) little difference between granulite and amphibolite facies types. Their REE patterns can be matched by models involving 5–15% partial melting of ultrabasic mantle with 3 times chondritic REE abundances, leaving a residue of olivine and orthopyroxene.