Rare earth and trace element geochemistry of a fragment of jurassic seafloor,Point Sal,California

A suite of rocks from the Point Sal ophiolite, California, were analyzed for rare earth elements (REE), Sc, Co, Na₂O, Cr, Zn and FeO. The lavas all have either flat or slightly light REE (LREE) depleted profiles relative to chondrites. The lavas contain smectite or greenschist facies mineralogy and some have radiogenically enriched ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios. This is interpreted as evidence of basaltseawater interaction (Hopsonet al., 1975; Davis and Lass, 1975). The smectite and zeolite bearing lavas that have been exposed to seawater for prolonged periods have anomalous Ce abundances. At higher grades of metamorphism, the lavas show no marked changes in light REE. The plutonic igneous rocks vary from early cumulus dunite to late stage, noncumulus diorite. All the plutonic rocks are light REE depleted with total REE abundance varying by a factor of 100 × between the dunites and diorites. Analyses of clinopyroxene and hornblende separates indicate that these two minerals strongly influence the REE characteristics of the early cumulates and late stage fractionates, respectively.In general, REE contents are: hornblende > clinopyroxene > plagioclase > orthopyroxene > olivine. Estimates of the REE compositions of parental lavas were obtained by calculating the REE contents of liquids in equilibrium with early cumulate clinopyroxenes. This reveals that the parent to the stratiform sequence was more depleted in light REE than the parent to the lava pile.     

Neodymium isotopic composition of Quaternary island arc lavas from Indonesia

${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios measured in Quaternary lavas from Java and the Banda arc of Indonesia range from 0.51242 to 0.51280 and exhibit an inverse correlation with ${}^{87}\text{Sr}{}^{86}\text{Sr}$. Isotopically, the Indonesian samples resemble Andean rather than island arc lavas. The samples from Java plot either within, or adjacent to the mantle array, towards higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios. Samples from the Banda arc and the anomalous calc-alkaline volcano Papandajan are characterized by relatively low ${}^{143}\text{Nd}{}^{144}\text{Nd}$ and high ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios. These characteristics are consistent with the interpretation that subducted terrigenous material was involved in the genesis of these lavas. Furthermore the Banda arc samples appear to lie on a mixing line between isotopic compositions characteristic of the mantle and upper continental crust. A high-K trachyte from the alkaline volcano Muriah, Java, has isotopic characteristics of the mantle (${}^{143}\text{Nd}{}^{144}\text{Nd}\text{= 0.51270}$, ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.70424}$), which implies that the extreme enrichment in large-ion-lithophile elements in its source must have occurred only shortly before its formation. The inferred ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratio of the unmodified mantle beneath Java and the Banda arc is lower than that observed in mid-ocean ridge basalt, which may have important implications for a better understanding of the geochemical structure of the mantle.     

Geochemical Constrains on Petrogenesis and Tectonic Setting of Volcanic Rocks from the Baimianxia and Sanwan Formations in the Northern Margin of the Yangtze Plate

On the basis of petrogeochemical data, the volcanic lavas of the Baimianxia Formation can be classified into two units: high TiO2 and low TiO2. The TiO2 concentration of the former is generally higher than 1%, which occurs in the lower part with high-grade metamorphism, but the latter is less than 1% and crops out in the upper part with low-grade metamorphism. The high-TiO2 unit is dominated by tholeiitic lavas showing high rare earth element (REE) contents (ΣREE?=?83.4–180.8?μg/g), high light/heavy REE (LREE/HREE) ratios (LREE/HREE=2.17–5.85) and weak negative Eu anomaly (Eu=0.79–1.01). Its trace element patterns display weak Nb-Ta anomalies with respect to Th, K, La, Ce, showing within-plate basalt affinities. In contrast, the low-TiO2 unit is characterized by low REE contents, low LREE/HREE ratios, and pronounced Nb-Ta anomalies, indicating typical arc or continental arc signature. Chondrite-normalized REE patterns of basalts and andesites from the Sanwan Formation are flat or LREE depletion, which is very similar to normal mid-oceanic basalt. Therefore, we suggest that these lavas should be formed in a back-arc basin setting. Sr-Nd isotopic data of the basalt in the lower part suggest that the rocks would have been formed in ~1144?Ma. Based on the geochemical and isotopic features of the basalts, we suggest that these rocks in the low part of the Baimianxia Formation should originate from an asthenospheric oceanic-island basalt-like mantle source, which may be produced by partial melting of garnet lherzolite, and significantly underwent fractional crystallization and crustal or lithospheric mantle contamination en route to the surface. However, laser ablation inductively coupled plasma mass spectrometry zircon U-Pb dating of the basalt sample from the upper part of the Baimianxia Formation gives a 437 Ma, indicating a Early Paleozoic age. The geochemical analysis in this paper suggests that they may originate from an arc or continental arc in response to aqueous fluids or melt expelled from a subducting slab, and the partial melting occurred in the garnet stability field. The samples of basalts and andesites in the Sanwan Formation show they are derived from depleted mantle source similar to normal mid-oceanic basalt. Finally, we can conclude that the lavas in the lower part of the Baimianxia Formation represent the geological records of rift-related volcanism in the middle Proterozoic, which is commonly considered to be the precursor of continental breakup and followed by oceanic basin forming from Neoproterozoic to early Paleozoic. Whereas, the lavas in upper part of the Baimianxia Formation and Sanwan Formations may have been generated by the oceanic and continental conversion that occurred in the early Paleozoic.     

Chemical characteristics of island-arc basalts: Implications for mantle sources

Major-element, trace-element and isotopic compositions of approximately 1200 basalts (< 53 wt. % SiO₂) from intra-oceanic island arcs have been compiled to assess the nature and possible sources of primitive island-arc basalts (IAB). The chemical characteristics of IAB are examined with reference to those of mid-ocean ridge basalts (MORB) and intraplate oceanic basalts (IPB). Major-element compositions of primitive [$\text{Mg}\text{(}\text{Mg +Fe}{}^{\mathrm{2+}}\text{)}\text{> 65}$] IAB and MORB are similar, but differ significantly from IPB. In general, IAB do not have higher Al₂O₃, lower TiO₂ or a lack of Fe enrichment compared to primitive MORB but many do have greater K₂O contents. Differences in major- and minor-element contents between more evolved IAB and MORB result from the dominance of plagioclase + olivine crystal fractionation in MORB magmas vs. clinopyroxene + olivine controlled fractionation in IAB suites. This difference in crystallization history may be related to the higher P_H2O or greater depth of crystallization of IAB magmas compared to those inferred for MORB.IAB are characteristically enriched in large-ion-lithophile (LIL) elements and depleted in high-field-strength ions (e.g., Zr, Nb and Hf) relative to normal MORB (N-type) and IPB. The enrichment of some LIL elements (e.g., Sr, Rb, Ba and Pb) relative to the rare-earth elements in IAB is difficult to explain by simple partial melting alone and suggests a multistage petrogenesis involving an LIL-enriched component. Low abundances of high-field-strength ions in evolved IAB are explicable in terms of fractional crystallization, but the cause for consistently low abundances in primitive IAB remains problematic.Island-arc lavas contain greater concentrations of volatiles and have higher $\text{CO}{}_2\text{H}{}_2\text{O}$ and Cl/F ratios than either MORB or IPB, suggesting involvement of a slab-derived volatile component. However, this is not consistent with ${}^3\text{He}{}^4\text{He}$ data which indicate that only near-trench volcanics have been significantly affected by dehydration of the oceanic crust.Sr-, Nd-, Pb- and O-isotopic data, in conjunction with the trace-element data, clearly indicate that IAB are derived from heterogeneous, LIL-depleted mantle sources most similar to those which give rise to enriched MORB (E-type). The marked shift towards higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ in IAB compared to oceanic lavas with similar ${}^{143}\text{Nd}{}^{144}\text{Nd}$ values cannot be explained simply by the addition of radiogenic Sr from the slab. Variable degrees of contamination from a crustally-derived sedimentary component is consistent with the isotopic and trace-element data from a number of arcs. However, the lack of correlation between LIL/REE ratios and more radiogenic isotopic ratios suggests that this enrichment/contamination process is complex. A multi-stage petrogenetic model involving subducted oceanic crust (± sediments), dehydration/volatile transfer, and partial melting of metasomatized mantle beneath island arcs is considered the most reasonable, although least constrained, method to generate a variety of primitive IAB.     

Chemical and isotopic evidence for mixing between depleted and enriched mantle,northwestern U.S.A.

Combined elemental and Sr, Nd, Pb and O isotopic data for late Cenozoic olivine tholeiite lavas from the northwestern Great Basin indicate derivation from at least two chemically and isotopically distinct mantle source regions with no significant modification by interaction with continental crust. The lack of crustal involvement is a direct reflection of the extensional tectonic environment which favors rapid ascent of magmas, minimal residence time in crustal magma chambers and scattered fissure eruptions.The observed chemical and isotopic variations in the tholeiite suite are attributed to mixing between depleted oceanic type mantle (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{~ 0.7030}$ and ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{~ 0.51305}$) and old, chemically heterogeneous, isotopically enriched subcontinental mantle (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{~ 0.7078}$ and ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{~ 0.51233}$). Model incompatible element concentrations suggest strong similarities between the depleted mantle and the mantles beneath normal oceanic ridge segments and back-arc basins and between the enriched mantle and the mantle beneath enriched oceanic ridge segments such as the Azores. Superimposed upon the characteristics derived from the two component mixing model may be the effects of a third mantle source which is identifiable only by its apparent radiogenic ${}^{206}\text{Pb}{}^{204}\text{Pb}$ ratios. If present, this third source may reflect a component derived from the downgoing slab of an ancient subduction zone.     

Rb—Sr and Sm—Nd geochronology of lower Proterozoic granite—greenstone terrains in French Guiana,South America

Nine samples of metavolcanic rock from the lower parts of greenstone belts in central French Guiana (the Paramaca series) and 14 granitic samples from the intrusive gneisses (the Degrad Roche and Arawa gneisses) were selected for Sm—Nd and Rb—Sr analysis.The Sm—Nd results from the metavolcanic series (including two tholeiites, five peridotitic komatiites and two andesites) yield an isochron age of 2.11±0.09 (2 σ) Ga with an initial ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratio (I_Nd) of 0.51002±9 (2 σ), corresponding to ?_Nd(T) = + 2.1 ± 1.8. This isochron is interpreted as representing the age of initial volcanism of the Paramaca series. Acid intrusives were dated by the Rb—Sr method. A whole rock Rb—Sr isochron, including data points from both the Degrad Roche and Arawa gneisses, yields an age of 2.00±0.07 (2 σ) Ga with initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio (I_Sr value) of 0.7019±4 (2 σ). This result is considered to be the time of emplacement of the orthogneiss protoliths.The positive ε_Nd value (+ 2.1 ± 1.8) obtained from the metavolcanic rocks of French Guiana suggests that their mantle sources have evolved in reservoirs slightly depleted in Light Rare Earth Elements (LREE). This result confirms the possible existence of ancient LREE-depleted reservoirs within the lower Proterozoic mantle. Moreover, the high ε_Nd(T) value for these rocks excludes any significant crustal contamination during magma genesis.The French Guianese orthogneisses yield a low I_Sr value (0.7019±4 (2 σ)) which, together with geochemical considerations, suggests that their granitic protoliths could have originated by partial melting of short-lived crustal precursors of basaltic to granodioritic composition.The present geochronological and isotopic study suggests that the Guiana Shield may represent a major continental accretion event during the lower Proterozoic.     

Columbia River volcanism: the question of mantle heterogeneity or crustal contamination

Basalts from the Columbia River flood basalt province of the northwestern U.S.A. show a large diversity in chemical and Nd and Sr isotopic compositions. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ranges from 0.51303 to 0.51208 and is strongly correlated with variations in ${}^{87}\text{Sr}{}^{86}\text{Sr}$. This correlation suggests mixing between two end member compositions, one characterized by ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{> 0.51303}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{< 0.7035}$, and the other with ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{< 0.5120}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{> 0.715}$. The more radiogenic component could be mantle enriched in incompatible elements during the Precambrian, or Precambrian materials of the continental crust. A quartz-rich xenolith found in the Columbia lavas has Rb-Sr and Sm Nd model ages of ≈ 1.4Æ, implying the existence of old, isotopically evolved crustal basement which could serve as contaminant. Nevertheless, crustal contamination alone cannot explain the chemical variation of the samples studied, and other fractionation processes must have occurred simultaneously. A model involving combined assimilation and crystal fractionation reproduces the chemical and isotopic characteristics of the volumetrically dominant Grande Ronde unit for an assumed crystallizing component of plagioclase, low calcium pyroxene and minor olivine. The data are not consistent with the suggestion that a ‘primordial’ mantle is the source for this continental flood basalt province. Rather they suggest that the main volume of these lavas was originally derived from a mantle similar in isotopic composition to island arc and ocean island basalts of the north Pacific. The primary magma was modified chemically and isotopically by crystal fractionation and assimilation of sialic crustal materials during its transport through, or storage in the continental crust.     

Isotopic and geochemical systematics in Tertiary-Recent basalts from southeastern Australia and implications for the evolution of the sub-continental lithosphere

Tertiary-Recent Tasmanian and Newer (Victoria/South Australia) basalts range from quartz tholeiite to olivine melilitite and show systematic increases in their incompatible element abundances with increasing degree of silica undersaturation. These two basalt provinces show similar relative abundances of rare earth elements (REE), differences in the relative concentrations of Rb, Ba, Th, K and Nb, and distinct, restricted isotopic compositions. The Tasmanian basalts have ${}^{87}\text{Sr}{}^{86}\text{Sr}$ from 0.7026 to 0.7034, and ?_Nd from + 7.5 to + 5.8; the Newer basalts have higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ from 0.7038 to 0.7045, and lower ?_Nd from +4.2 to + 1.7. The range in Sr and Nd isotope compositions can be denned by primary magma compositions for both provinces, using Mg-values, Ni content and the presence of spinel lherzolite nodules. Major and trace element and Sr, Nd and Pb isotope compositions are uniform on a scale of up to 50 km for four separate Newer basanite centers. The chemical and isotopic data are consistent with a model whereby tholeiitic basalts are derived by large degrees of partial melting from a chemically uniform but isotopically variable source, and generation of undersaturated, alkaline basalts by smaller degrees of partial melting of the same source. No isotopic or geochemical evidence was found which would suggest that the more evolved basalts have been contaminated by continental crust.In contrast to tholeiitic and alkalic basalts from Hawaii, there is a continuous spectrum of isotope compositions for the Newer tholeiitic to alkalic basalts. A model is proposed for the generation of these basalts involving mixtures of hotspot mantle plume-derived melt and lithospheric mantle-derived melt, where observed differences between ocean island and continental alkaline basalts are attributed to differences between the sub-oceanic and sub-continental lithospheric mantles. Isotopic differences between tholeiitic and alkalic basalts are interpreted to be due to varying degrees of exchange and mixing between the hotspot plume and lithospheric mantle melt components. The model is consistent with the generation of these basalts from a source which has been recently enriched in the LREE.     

The geochemistry of mantle chromitites from the northern part of the Oman ophiolite: inferred parental melt compositions

Chromitites from a single section through the mantle in the Oman ophiolite are of two different types. Low-cr# chromitites, of MORB affinity are found in the upper part of the section, close to the Moho. High-cr# chromitites, with arc affinities are found deeper in the mantle. Experimental data are used to recover the compositions of the melts parental to the chromitites and show that the low-cr# chromitites were derived from melts with 14.5–15.4 wt% Al₂O₃, with 0.4 to 0.9 wt% TiO₂ and with a maximum possible mg# of 0.76. In contrast the high-cr# chromitites were derived from melts with 11.8–12.9 wt% Al₂O₃, 0.2–0.35 wt% TiO₂ and a maximum melt mg# of 0.785. Comparison with the published compositions of lavas from the Oman ophiolite shows that the low-cr# chromitites may be genetically related to the upper (Lasail, and Alley) pillow lava units and the high-cr# chromitites the boninites of the upper pillow lava Alley Unit. The calculated TiO₂–Al₂O₃ compositions of the parental chromitite magmas indicate that the high-cr# chromitites were derived from high-Ca boninitic melts, produced by melting of depleted mantle peridotite. The low-cr# chromitites were derived from melts which were a mixture of two end-members—one represented by a depleted mantle melt and the other represented by MORB. This mixing probably took place as a result of melt–rock reaction. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Sm-Nd in marine carbonates and phosphates: Implications for Nd isotopes in seawater and crustal ages

This study explores the possibility of establishing Nd isotopic variations in seawater over geologic time. Calcite, aragonite and apatite are examined as possible phases recording seawater values of ?_Nd. Modern, biogenic and inorganically precipitated calcite and aragonite from marine environments were found to have Nd concentrations of from 0.2 to 70 ppb, showing that primary marine CaCO₃ contains little REE and that Nd/Ca is not greatly enhanced relative to seawater during carbonate precipitation. Very young marine limestone and dolomite containing no continental detritus have ~200 ppb Nd. All the carbonates are LREE enriched ($\text{?0.16 ≤f}{}^{\mathrm{<mtext>Sm</mtext><mtext>Nd</mtext>}}\text{≤?0.45}$). Modern and very young Atlantic and Pacific carbonates have ?_Nd in the range of shallow Atlantic and Pacific seawater respectively, implying that they derive their REE from local seawater. The Nd in well preserved carbonate fossils is ≤4 × 10⁴ ppb, much greater than in their modern counterparts but like the high values found for carbonates in other studies. We believe the high REE contents (at the 500 ppb level) in some detritusfree carbonates are due to REE-rich Fe-hydroxide in/on the carbonate. In favorable cases, such material may record seawater ?_Nd values, however introduction of extraneous REE may obscure the original isotopic composition of pure CaCO₃ because of its very low intrinsic primary REE abundance.Modern biogenic apatite is also shown to have very low REE content (<150 ppb Nd) but appears to quickly scavenge REE from seawater. Inorganically precipitated apatite from phosphorites has high concentrations of seawater-derived REE. Young phosphorite apatite from the Atlantic and Pacific oceans has ?_Nd in the range of the seawater from these oceans. Older apatite samples of similar age from different localities bordering common oceans record similar values of ?_Nd(T). Sedimentary apatite has ?_Sr(T) values in good agreement with the curves for ${}^{87}\text{Sr}{}^{86}\text{Sr}$ of seawater as a function of time. Individual conodonts from a single formation yield the same ?_Sr(T) and ?_Nd(T). Other workers have shown that sedimentary apatite preserves seawater REE patterns. These characteristics suggest that sedimentary apatite can be used to determine ?_Nd(T) in ancient seawater. The seawater values so inferred range between ?1.7 and ?8.9 over the last 700 my and lie in the range of modern seawater, showing no evidence for drastic changes. High values of seawater ?_Nd(T) in the Triassic and latest Precambrian may correlate with the breakup of large continental landmasses. The initial ?_Nd(T) =?15.0 of a 2 AE old phosphorite implies the presence of ~ 1.5 AE old continental crust at 2 AE ago. The approach outlined here can be used to constrain the age of the exposed crust as a function of time.     

Geochemistry of the Archean Yellowknife Supergroup

The Archean Yellowknife Supergroup (Slave Structural Province. Canada) is composed of a thick sequence of supracrustal rocks, which differs from most Archean greenstone belts in that it contains a large proportion ( ~ 80%) of sedimentary rocks. Felsic volcanics of the Banting Formation are characterized by HREE depletion without Eu-anomalies, indicating an origin by small degrees of partial melting of a mafic source, with minor garnet in the residua. Granitic rocks include synkinematic granites [HREE-depleted; low (${}^{87}\text{Sr}{}^{86}\text{Sr}$)_I], post-kinematic granites [negative Eu-anomalies, high (${}^{87}\text{Sr}{}^{86}\text{Sr}$)_I] and granitic gneisses with REE patterns similar to the post-kinematic granites. Sedimentary rocks (turbidites) of the Burwash and Walsh Formations have similar chemical compositions and were derived from 20% mafic-intermediate volcanics, 55% felsic volcanics and 25% granitic rocks. Jackson Lake Formation lithic wackes can be divided into two groups with Group A derived from 50% mafic-intermediate volcanics and 50% felsic volcanics and Group B, characterized by HREE depletion, derived almost exclusively from felsic volcanics.REE patterns of Yellowknife sedimentary rocks are similar to other Archean sedimentary REE patterns, although they have higher $\text{La}{}_{\mathrm{N}}\text{Yb}{}_{\mathrm{N}}$. These patterns differ significantly from typical post-Archean sedimentary REE patterns, supporting the idea that Archean exposed crust had a different composition than the present day exposed crust.     

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.     

Importance of the Lu-Hf isotopic system in studies of planetary chronology and chemical evolution

The ¹⁷⁶Lu-¹⁷⁶Hf isotope method and its applications in earth sciences are discussed. Greater fractionation of Lu/Hf than Sm/Nd in planetary magmatic processes makes ${}^{176}\text{Hf}{}^{177}\text{Hf}$ a powerful geochemical tracer. In general, proportional variations of ${}^{176}\text{Hf}{}^{177}\text{Hf}$ exceed those of ${}^{143}\text{Nd}{}^{\mathrm{l44}}\text{Nd}$ by factors of 1.5–3 in terrestrial and lunar materials. Lu-Hf studies therefore have a major contribution to make in understanding of terrestrial and other planetary evolution through time, and this is the principal importance of Lu-Hf. New data on basalts from oceanic islands show unequivocally that whereas considerable divergences occur in ${}^{176}\text{Hf}{}^{177}\text{Hf}\text{-}{}^{87}\text{Sr}{}^{86}\text{Sr}$ and ${}^{143}\text{Nd}{}^{\mathrm{l44}}\text{Nd}\text{-}{}^{87}\text{Sr}{}^{86}\text{Sr}$ diagrams, ${}^{176}\text{Hf}{}^{177}\text{Hf}$ and ${}^{143}\text{Nd}{}^{144}\text{Nd}$ display a single, linear isotopic variation in the suboceanic mantle. These discordant ${}^{87}\text{Sr}{}^{86}\text{Sr}$ relationships may allow, with the acquisition of further Hf-Nd-Sr isotopic data, a distinction between processes such as mantle metasomatism, influence of seawater-altered material in the magma source, or recycling of sediments into the mantle. In order to evaluate the Hf-Nd isotopic correlation in terms of mantle fractionation history, there is a need for measurements of Hf distribution coefficients between silicate minerals and liquids, and specifically for a knowledge of Hf behavior in relation to rareearth elements. For studying ancient terrestrial Hf isotopic variations, the best quality Hf isotope data are obtained from granitoid rocks or zircons. New data show that very U-Pb discordant zircons may have upwardly-biased ${}^{176}\text{Hf}{}^{177}\text{Hf}$, but that at least concordant to slightly discordant zircons appear to be reliable carriers of initial ${}^{176}\text{Hf}{}^{177}\text{Hf}$. Until the controls on addition of radiogenic Hf to zircon are understood, combined zircon-whole rock studies are recommended. Lu-Hf has been demonstrated as a viable tool for dating of ancient terrestrial and extraterrestrial samples, but because it offers little advantage over existing methods, is unlikely to find wide application in pure chronological studies.     

Noble gases in E-chondrites

Noble gas data are reported for 12 E-chondrites. Combined with literature data, they show that K-Ar ages are >4 Æ for 14 out of 18 meteorites, yet U, Th-He ages are often shorter, perhaps due to late, mild reheating. Cosmic-ray exposure ages differ systematically between types 4 and 6, with E4's mostly below 16 Myr and E6's above 30 Myr. This may mean that the E-chondrite parent body contains predominantly a single petrologic type on the (~ 1 km) scale of individual impacts, in contrast to the more thoroughly mixed parent bodies of the ordinary chondrites.The heavy noble gases consist of at least two primordial components: the usual planetary component (${}^{36}\text{Ar}{}^{132}\text{Xe}\text{~ 80}$) and a less fractionated, ‘subsolar’ component ($\text{2700 ≤}{}^{36}\text{Ar}{}^{132}\text{Xe}\text{≤ 3800}$). The latter is found in highest concentration in the E4 chondrite South Oman (³⁶Ar = 760 × 10^?8cc/g, ${}^{36}\text{Ar}{}^{132}\text{Xe}\text{= 2700}$). The isotopic compositions of both components are similar to typical planetary values, indicating that some factor other than mass controlled the noble gas elemental ratios. The heavy Xe isotopes occasionally show some of the lowest ${}^{134}\text{Xe}{}^{132}\text{Xe}$ and ${}^{136}\text{Xe}{}^{132}\text{Xe}$ ratios measured in bulk chondrites, suggestive of nearly fission-free Xe (e.g. ${}^{136}\text{Xe}{}^{132}\text{Xe}\text{= 0.3095 ± 0.0020}$). Amounts of planetary gas in E4 E6 chondrites fall in the range for ordinary chondrites of types 4–6, but, in contrast to the ordinary chondrites. fail to correlate with petrologic type or volatile trace element contents. Another unusual feature of E-chondrites is that primordial Ne is present even in most 4's and 5's (²⁰Ne_p ~ 1 to 7 × 10^?8cc/g). with an isotopic composition consistent with planetary Ne.Analyses of mineral separates show that the planetary gases are concentrated in an HF- and HCl-insoluble mineral similar to phase Q, the poorly characterized, HNO₃-soluble carrier of primordial gases in carbonaceous and ordinary chondrites. The subsolar gases, on the other hand, are located in an HCl- and HNO₃-resistant phase, possibly enstatite or a minor phase included in enstatite. Much of the ¹²⁹Xe_r (50% for E4's, > 70% for E6's) is in HCl-resistant but HF-soluble sites, suggestive of a silicate.A similar subsolar component may be responsible for the high ${}^{36}\text{Ar}{}^{132}\text{Xe}$ ratios of some C3's, unequilibrated ordinary chondrites, and the unique aubrite Shallowater. The planet Venus also has a high $\text{Ar}\text{Kr}$ ratio, well above the planetary range, and hence may have acquired its noble gases from an E-chondrite-like material, similar to South Oman.     

Strontium isotopic studies of the volcanic rocks of the Saunda arc,Indonesia, and their petrogenetic implications

Pleistocene and Recent lavas from the Sunda arc range from those showing affinities with the island arc tholeiitic series, through a spectrum of calc-alkaline to high-K alkaline rocks. The tholeiitic rocks have relatively low ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios averaging 0–7043; the calc-alkaline rocks show a wide range (from 0.7038 to 0.7059, averaging 0.7048); the high-K alkaline rocks average 0.7045. A rhyolitic ignimbrite from Sumatra has an ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of 0.7139.The relationship between ${}^{87}\text{Sr}{}^{86}\text{Sr}$ and major and trace element geochemistry is variable and complex. Lavas from the same volcano sometimes show significant differences in ${}^{87}\text{Sr}{}^{86}\text{Sr}$ despite close geochemical relationships. Rocks of the calc-alkaline suite show a regular decrease in ${}^{87}\text{Sr}{}^{86}\text{Sr}$ from West Java to Bali and there is some evidence for increasing ${}^{87}\text{Sr}{}^{86}\text{Sr}$ with increasing depth to the Benioff zone. Calc-alkaline and tholeiitic rocks from the Sunda arc have significantly higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios than those from other island arcs, except from those arcs where continental crustal involvement has been inferred (e.g. New Zealand).A model of ⁸⁷Sr enrichment due to isotopic equilibration of oceanic crust with sea water and disequilibrium melting in the slab and/or mantle is favoured to explain the Sr isotopic composition of the tholeiitic and normal calc-alkaline lavas. Calc-alkaline lavas with high ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios are best explained by either sialic contamination, or the presence of alkali basalt as a component of the downgoing slab. The Sr isotopic data for the high-K alkaline lavas suggest a mantle origin. The high ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio in the Lake Toba rhyolite implies a crustal origin.     

Mid-Proterozoic Plume-Related Thermal Event in Eastern Indian Craton: Evidence from Trace Elements,REE Geochemistry and Sr - Nd Isotope Systematics of Basic-Ultrabasic Intrusives from Dalma Volcanic Belt

Trace, REE, Sr and Nd isotopic studies have been carried out on gabbro-pyroxenite intrusives (Rb-Sr isochron age ∼ 1619±38 Ma; Sr_i ∼ 0.70552±0.00002) of the Dalma volcanic belt from eastern Indian craton. Primitive mantle-normalised trace element patterns show a general depletion of high field strength elements and LREE but more or less flat pattern in most compatible elements. Chondrite-normalised REE plots show depleted LREE-flat HREE patterns [(SLREE/SHREE)_N < 1, (Ce/Yb)_N < 1] strikingly similar to the komatiitic and tholeiitic lavas from this belt. Nd isotopic data with mean f_Sm/Nd ∼ +0.2704 and high e_Nd (mean +7.8) values indicate that the source of these rocks was depleted in LREE for considerably long time. When plotted on the global e_Nd evolution path for the upper mantle the Dalma intrusives fall exactly around the depleted MORB-type mantle at 1.6 Ga.Enrichment in some LILE like Rb, Ba, Th is found both in the tholeiitic lavas and the residues indicating them to be source characteristics. Positive DNb values of most of the mafic-ultramafic units (including komatiitic lavas) of this belt indicate that they originated from a mantle plume with thick envelope of hot upper mantle producing MORB-like depleted komatiites, tholeiites and intrusives. The mid-Proterozoic plume eventually rifted the continent above, forming a rapidly subsiding basin which was subsequently collapsed and compressed. The plume also caused widespread thermal events recorded in charnockitisation, migmatisation and granitisation around 1.6 Ga. This was possibly part of a global ∼1.6 Ga thermal anomaly which affected the pre-existing large landmass comprising atleast Antarctica, Australia and India (Mawson continent?).     

Trace element partitioning and melt structure: An experimental study at 1 atm pressure

Diopside-melt and forsterite-melt rare earth (REE) and Ni partition coefficients have been determined as a function of bulk compositions of the melt. Available Raman spectroscopic data have been used to determine the structures of the melts coexisting with diopside and forsterite. The compositional dependence of the partition coefficients is then related to the structural changes of the melt.The melts in all experiments have a ratio of nonbridging oxygens to tetrahedral cations ($\text{NBO}\text{T}$) between 1 and 0. The quenched melts consist of structural units that have, on the average, 2 (chain), 1 (sheet) and 0 (three-dimensional network) nonbridging oxygens per tetrahedral cation. The proportions of these structural units in the melts, as well as the overall $\text{NBO}\text{T}$, change as a function of the bulk composition of the melt.It has been found that Ce, Sm, Tm and Ni crystal-liquid partition coefficients ($\text{K}{}^{\mathrm{crystal?liq}}{}_{\mathrm{i}}\text{=}\text{C}{}^{\mathrm{crystal}}{}_{\mathrm{i}}\text{C}{}^{\mathrm{liq}}{}_{\mathrm{i}}$) decrease linearly with increasing $\text{NBO}\text{T}$. The values of the individual REE crystal-liquid trace element partition coefficients have different functional relations to $\text{NBO}\text{T}$, so that the degree of light REE enrichment of the melts would depend on their $\text{NBO}\text{T}$.The solution mechanisms of minor oxides such as CO₂, H₂O, TiO₂, P₂O₅ and Fe₂O₃ in silicate melts are known. These data have been recast as changes of $\text{NBO}\text{T}$ of the melts with regard to the type of oxide and its concentration in the melt. From such data the dependence of crystal-liquid partition coefficients on concentration and type of minor oxide in melt solution has been calculated.     

Rutile solubility and titanium coordination in silicate melts

The solubility of rutile has been determined in a series of compositions in the K₂O-Al₂O₃-SiO₂ system ($\text{K}{}^1\text{=}\text{K}{}_2\text{O}\text{(K}{}_2\text{O}$ + Al₂O₃) = 0.38–0.90), and the CaO-Al₂O₃-SiO₂ system ($\text{C}{}^1\text{=}\text{CaO}\text{(CaO + Al}{}_2\text{O}{}_3\text{)}\text{= 0.47–0.59}$). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the $\text{K}{}^1$ ratio. For example, at 1475°C the amount of TiO₂ required for rutile saturation varies from 9.5 wt% ($\text{K}{}^1\text{= 0.38}$) to 11.5 wt% ($\text{K}{}^1\text{= 0.48}$) to 41.2 wt% ($\text{K}{}^1\text{= 0.90}$). In the CAS system at 1475°C, rutile solubility is not a strong function of $\text{C}{}^1$. The amount of TiO₂ required for saturation varies from 14 wt% ($\text{C}{}^1\text{= 0.48}$) to 16.2 wt% ($\text{C}{}^1\text{= 0.59}$).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K⁺ in excess of that needed to charge balance Al³⁺. The suggested stoichiometry of this complex is K₂Ti₂O₅ or K₂Ti₃O₇. In CAS melts, the data suggest that Ca²⁺ in excess of A1³⁺ is not as effective at complexing with Ti as is K⁺. The greater solubility of rutile in CAS melts when $\text{C}{}^1$ is less than 0.54 compared to KAS melts of equal $\text{K}{}^1$ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiK_β x-ray emission spectra of KAS glasses ($\text{K}{}^1\text{= 0.43–0.60}$) with 7 mole% added TiO₂, rutile, and Ba₂TiO₄, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba₂TiO₄, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.