CaAl ratio and composition of the Earth's upper mantle

Undifferentiated meteorites (chondrites) have the same relative abundances of refractory lithophile elements (Ca, Al, Ti, Sc, REE, etc.), despite variable absolute concentrations. The reasonable assumption of chondritic ratios among refractory elements in the bulk Earth is used to constrain the chemical composition of the upper mantle in the following way: Correlations of the compatible refractory elements Ca, Al, Ti, Sc and Yb with MgO are worldwide very similar in suites of spinel-lherzolite xenoliths from basaltic rocks. Such suites represent upper mantle material depleted to differing degrees by extraction of partial melts. From these refractory elements vs. MgO correlations, ratios of pairs of refractory elements were calculated at various MgO contents. Chondritic $\text{Al}\text{Ti}$ and $\text{Sc}\text{Ti}$ ratios were only obtained for MgO contents below 36%. A chrondritic $\text{Sc}\text{Yb}$ ratio requires an MgO content above 35%. We therefore accept 35.5% as the most reasonable MgO content of undepleted upper mantle. This MgO content is slightly below the spinel-lherzolite with the lowest measured MgO content (36.22%). The corresponding Al₂O₃ content of 4.75% is higher than in previous estimates of upper mantle composition. The concentrations of other elements were obtained from similar correlations at a MgO content of 35.5%. The resulting present upper mantle composition is enriched in refractory elements by a factor of 1.49 relative to Si and Cl and by a factor of 1.12 for Mg relative to Si and Cl. These enrichments are in the same range as those for the Vigarano type carbonaceous chondrites. The Mg/Mg + Fe ratio of 89 is slightly lower than previous estimates.The $\text{Ca}\text{Al}$ ratio in spinel lherzolite suites is, however, uniformly higher worldwide than the chondritic ratio by about 15%. Orogenic peridotites as well as komatiites appear to have similar non-chondritic $\text{Ca}\text{Al}$ ratios. It is therefore suggested that this non-chondritic $\text{Ca}\text{Al}$ ratio is a characteristic of the upper mantle, possibly since the Archean. A minor fractionation of about 4% of garnet in an early, global melting event (deep magma ocean?) is presented as the most likely cause for the high $\text{Ca}\text{Al}\text{-}\text{ratio}$. In this case the addition of 4% of such a garnet component to the undepleted present upper mantle would be required to obtain the composition of the primordial upper mantle. The $\text{Ca}\text{Al}\text{-}\text{ratio}$ of this primordial mantle would be 15% higher than that of the undepleted present upper mantle, resulting in an enrichment of refractory elements of 1.70 ($\text{Al}\text{Si}$ relative to Cl) for the primordial upper mantle.     

Siderophile element abundances in the upper mantle: evidence for a sulfide signature and equilibrium with the core

Measurements of the intrinsic oxygen fugacities of samples from the Earth's upper mantle have shown that the characteristic oxidation state ranges from values close to Fe-Ni metal saturation to more oxidized values. Tectonic processes can account for the progressive and variable oxidation of a mantle that was originally in equilibrium with metal, so that the oxygen fugacity data give strong support to the possibility of protocore -protomantle equilibrium. The data for apparently overabundant siderophile elements in the mantle are reviewed and 2 groups (Group A = Ge, Au, Pd, Pt, Ru, Rh, Ir, Re, Os; Group B = Sn, Sb, Ag, Ga, Cu, As, Co, Ni, W, Mo) are recognized. Group A abundances result from an overprinting, by a late-accreting chondritic component, of a mantle that had suffered major extraction of the indigenous complement by core-forming metal (Chou, 1978). Group B, however, are ≈- 10 × more abundant than Group A and may be distinguished as a group by their greater chalcophile tendencies. This is highlighted, for example, by the large Cl-normalized Sn/Ge ratio of the mantle, which is unexpected as a result of metal-silicate fractionation alone, but can be accounted for if some Sn. together with sulfur was retained in the mantle during core separation. Industrial experience in the equilibrium of molten Fe and silicate slags shows that sulfur is not overwhelmingly partitioned into metal so that the concept of partial (≈-20% of original accreting component) retention of sulfur and Group B elements in the mantle has experimental and theoretical support. Following core separation, progressive loss of sulfide from the mantle is indicated by the anomalously high Ni (at a given Mg-number) in Archaean basalts and siliceous, Mg-poor sediments. It is also a feature of oceanic and continental basalts that some U/Pb fractionation must have occurred in the mantle source regions following core separation, and this is most satisfactorily achieved if Pb is partially removed from U in a sulfide phase.     

Volatiles in basalts and andesites from the Galapagos Spreading Center, 85° to 86°W

Glasses from submarine lavas recovered by the ALVIN submersible from the Galapagos Spreading Center (GSC) near 86°W have been analyzed by electron microprobe for major elements and by high-temperature mass spectrometry for volatiles. The samples studied range in composition from basalt to andesite and are more evolved than typical MORBs. Previous studies indicate that they are related to normal MORB by extensive crystal fractionation in small, isolated magma chambers. The H₂O, Cl and F contents of these lavas are substantially higher than any previously reported for MORBs. H₂O, Cl and F abundances increase linearly with P₂O₅ content, which is used as an indicator of the extent of crystal fractionation. The $\text{Fe}{}_2\text{O}{}_3\text{(FeO + Fe}{}_2\text{O}{}_3\text{)}$ ratios measured in the andesite glasses progressively decrease with increasing P₂O₅ content and are probably related to fractionation of Fe-Tioxides. Reduced carbon gas species, principally CH₄ and CO, were discovered in these glasses. The presence of reduced carbon species in GSC glasses may be indicative of a more reduced oxidation state of the upper mantle than is commonly assumed.     

Platinum group element geochemistry of komatiites from the Alexo and Pyke Hill areas, Ontario, Canada

Thirty-three whole-rock drill core samples and thirteen olivine, chromite, and sulfide separates from three differentiated komatiite lava flows at Alexo and Pyke Hill, Canada, were analyzed for PGEs using the Carius tube digestion ID-ICP-MS technique. The emplaced lavas are Al-undepleted komatiites with ∼27% MgO derived by ∼50% partial melting of LILE-depleted Archean mantle. Major and minor element variations during and after emplacement were controlled by 30 to 50% fractionation of olivine Fo_93-94. The emplaced lavas are characterized by (Pd/Ir)_N = 4.0 to 4.6, (Os/Ir)_N = 1.07, and Os abundances of ∼2.3 ppb. Variations in PGE abundances within individual flows indicate that Os and Ir were compatible (bulk D_Os,Ir = 2.4-7.1) and that Pt and Pd were incompatible (bulk D_Pt,Pd < 0.2) during lava differentiation, whereas bulk D_Ru was close to unity. Analyses of cumulus olivine separates indicate that PGEs were incompatible in olivine (D_PGEs^Ol-Liq = 0.04-0.7). The bulk fractionation trends cannot be accounted for by fractionation of olivine alone, and require an unidentified Os-Ir-rich phase. The composition of the mantle source (Os = 3.9 ppb, Ir = 3.6 ppb, Ru = 5.4 ppb, Pt and Pd = 5.7 ppb) was constrained empirically for Ru, Pt, and Pd; the Os/Ir ratio was taken to be identical to that in the emplaced melt, and the Ru/Ir ratio was taken to be chondritic, so that the absolute IPGE abundances of the source were determined by Ru. This is the first estimate of the PGE composition of a mantle source derived from analyses of erupted lavas. The suprachondritic Pd/Ir and Os/Ir of the inferred Abitibi komatiite mantle source are similar to those in off-craton spinel lherzolites, orogenic massif lherzolites, and enstatite chondrites, and are considered to be an intrinsic mantle feature. Bulk partition coefficients for use in komatiite melting models derived from the source and emplaced melt compositions are: D_Os,Ir = 2.3, D_Ru = 1.0, D_Pt,Pd = 0.07. Ruthenium abundances are good indicators of absolute IPGE abundances in the mantle sources of komatiite melts with 26 to 29% MgO, as Ru fractionates very little during both high degrees of partial melting and lava differentiation.     

Volatile contents and ferric-ferrous ratios of basalt,ferrobasalt, andesite and rhyodacite glasses from the Galapagos 95.5°W propagating rift

Volatiles and major elements in abyssal glasses ranging in composition from basalt, ferrobasalt, andesite to rhyodacite from the Galapagos Spreading Center (GSC) near 95°W were analyzed using electron microprobe and high temperature mass spectrometry. Total volatile content ranged from 0.32 wt.% to 2.74 wt.%. Volatile abundances of MORB glasses from the 95.5°W propagating rift are similar to those from the adjacent normal rift (avg. 0.34 wt.%) and lower than those of N-type MORB from the Mid-Atlantic Ridge (avg. 0.49 wt.%). Although both propagating and non-propagating rift glasses contain trace amounts of methane (<0.01 wt.%) and carbon monoxide (0.04 wt.%), significantly higher 100 $\text{Fe}{}_2\text{O}{}_3\text{FeO}\text{+ Fe}{}_2\text{O}{}_3$ ratios are observed for the primitive propagating rift glasses. Water contents of the most primitive GSC glasses are ~0.09 wt.% suggesting a water content for the mantle source of ~0.02 wt.% which indicates that source masses with very low water content can be involved in the generation of MORB.In fractionated ferrobasalt, andesite and rhyodacite glasses from the 95.5°W propagating rift, increasing abundances of H₂O, Cl and F indicate highly incompatible behavior, whereas CO₂ and reduced carbon species appear to decrease in abundance with increasing differentiation. Ferric-ferrous ratios increase from basalt to andesite and reduce to near zero in the rhyodacite. These values are not distinguishable from those previously reported for similar fractionated glasses from the Galapagos 85°W propagating rift, despite the apparent suppression of oxide precipitation in the 85°W suite.     

Solar-system abundances of the elements

A new abundance table has been compiled, based on a critical review of all C1 chondrite analyses up to mid-1982. Where C1 data were inaccurate or lacking, data for other meteorite classes were used, but with allowance for fractionation among classes. In a number of cases, interelement ratios from meteorites or lunar and terrestrial rocks as well as solar wind were used to check and constrain abundances. A few elements were interpolated (Ar, Kr, Xe, Hg) or estimated from astronomical data (H, C, N, O, He, Ne).For most elements, the new abundances differ by less than 20% from those of Cameron (1982a). In 14 cases, the change is between 20 and 50% (He, Ne, Be, Br, Nb, Te, I, Xe, La, Gd, Tb, Yb, Ta and Pb) and in 5 others, it exceeds 50% (B, P, Mo, W, Hg). Some important interelement ratios ($\text{Na}\text{K}$, $\text{Se}\text{Te}$, $\text{Rb}\text{Sr}$, $\text{Kr}\text{Xe}$, $\text{La}\text{W}$, $\text{Th}\text{U}$, $\text{Pb}\text{U}$, etc.) are significantly affected by these changes.Three tests were carried out, to see how closely C1 chondrites approximate primordial solar system abundances. (1) A plot of solar vs Cl abundances shows only 7 discrepancies by more than twice the nominal error of the solar abundance: Ga, Ge, Nb, Ag, Lu, W and Os. Most or all apparently reflect errors in the solar data or f-values. (2) The major cosmochemical groups (refractories, siderophiles, volatiles, etc.) show no significant fractionation between the Sun and C1's, except possibly for a slight enrichment of volatiles in Cl's. (3) Abundances of odd-A nuclides between A = 65 and 209 show an almost perfectly smooth trend, with elemental abundances conforming to the slope defined by isotopic abundances. There is no evidence for systematic fractionation of the major cosmochemical groups from each other. Small irregularities (10–15%) show up in the Ag-Cd-In and Sm-Eu regions; the former may be due to a ~ 15% error in the Ag abundance and the latter, to a 10–20% fractionation of Eu during condensation, to contamination of C1 chondrites with interplanetary dust during regolith exposure, or to a change from s-process to r-process dominance.It appears that the new set of abundances is accurate to at least 10%, as irregularities of 5–10% are readily detectable. Accordingly, Cl chondrites seem to match primordial solar-system matter to ? 10%, with only four exceptions. Br and I are definitely and B is possibly fractionated by hydrothermal alteration, whereas Eu seems to be enriched by nebular condensation or regolith contamination.     

Rare earth element geochemistry of the Betts Cove ophiolite,Newfoundland: complexities in ophiolite formation

The Betts Cove ophiolite includes the components of typical ocean crust: pillow lavas, sheeted dikes, gabbros and ultramafics. However, the trace element geochemistry of basaltic rocks is unusual. Three geochemical units are recognized within the lava and dike members. Within the pillow lavas, the geochemical units correspond to stratigraphic units. Upper lavas have ‘normal’ (i.e., typical for ocean floor basalts) TiO₂ contents (0.75 to 2.0 wt%), heavy rare earth elements (HREE) values in the range 6–20× chondrites and chondrite-normalized REE patterns with relative LREE depletion. Intermediate lavas have TiO₂ contents between 0.30 and 0.50 wt%, HREE contents from 4–7× chondrites and extreme relative LREE depletion. Lower lavas have anomalously low TiO₂ contents (<0.30 wt%) and unusual convex-downwards REE patterns with REE abundances around 2–5 × chondrite. These geochemical differences can be explained if the three groups were derived from different mantle sources. Independent mantle sources for the three units are consistent with their different ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios varying at 480 m.y.B.P. from 0.51222 in a lower lava to 0.51238 in an upper lava. The upper lavas may be partial melts of a source similar in composition to that of modern MORB, the intermediate lavas may be from a very depleted oceanic mantle (second stage melt), and the lower lavas may have formed by melting an extremely depleted mantle that had been invaded by a LREE-enriched fluid. A possible tectonic environment where these different sources could be juxtaposed is a back-arc or inter-arc basin.     

Ries impact crater,southern Germany: search for meteoritic material

Twenty-three samples from the Ries crater, representing a wide range of shock metamorphism, were analyzed for seven siderophile elements (Au, Ge, Ir, Ni, Os, Pd, Re) and five volatile elements (Ag, Cd, Sb, Se, Zn). Taking Ir as an example, we found siderophile enrichments over the indigenous level of 0.015 ppb Ir occur in only eight samples. The excess is very modest; even the most enriched samples (a weakly shocked biotite gneiss and a metal-impregnated amphibolite) have Ir, Os corresponding to ~4 × 10^?4 C1 chondrite abundances. Of five flädle glasses analyzed only one shows excess Ir. Suevite matrix and vesicular glass have slight enrichment, but homogenous glass from the same rock does not. In flädle glasses, Ni and Se are strongly correlated and apparently reside in Ir, Os-poor Sulfides [pyrrhotite, chalcopyrite, pentlandite(?)]of terrestrial, probably sedimentary, origin. The Ir, Os and Ni enrichments of the metal-bearing amphibolite are compatible with chondritic ratios, but these are ill-defined because of uncertainty in Ni. In the other samples enriched in siderophiles Ir(Os), Ni and Se are mutually correlated; $\text{Ni}\text{Ir}$ and $\text{Ni}\text{Os}$ ~ 11 × C1 and are much higher than any chondritic ratios; $\text{Se}\text{Ni}\text{~ 2 × C1}$ and suggests a sulfide phase, rather than metal may be the host of the correlated elements. Lacking a plausible local source, this material is apparently meteoritic in origin. The unusual elemental ratios, coupled with the very low enrichments, tend to exclude chondrites and most irons as likely projectile material. Of the achondrites, aubrites seem slightly preferable. Ratios of excess siderophiles in Ries materiel match tolerably those of an aubrite (possibly atypical) occurring as an inclusion in the Bencubbin meteorite, Australia. The Hungaria group of Mars-crossing asteroids may be a source of aubritic projectiles.     

Siderophile elements in Martian meteorites and implications for core formation in Mars

Noble metals, Mo, W, and 24 other elements were determined in six SNC meteorites of presumably Martian origin. Based on element correlations, representative siderophile element concentrations for the silicate mantle of Mars were inferred. From a comparison with experimentally determined metal/silicate partition coefficients of the moderately siderophile elements: Fe, Ni, Co, W, Mo, and Ga, it is concluded that equilibrium between core forming metal and silicates in Mars has occurred at high temperatures (around 2200°C) and low pressures (<1 GPa). This suggests that metal segregation occurred concurrently with rapid accretion of Mars, which is consistent with the inference from excess ¹⁸²W in Martian meteorites (Lee and Halliday, 1997). Concentrations of Ir, Os, Ru, Pt, and Au in the analyzed Martian meteorites, except ALH84001, are at a level of approximately 10⁻²–10⁻³ × CI. The comparatively high abundances of noble metals in Martian meteorites require the addition of chondritic material after core formation. The similarity in Au/La and Pt/Ca ratios between ALH84001 and the other Martian meteorites suggests crystallization of ALH84001 after complete accretion of Mars.     

A major element,PGE and Re–Os isotope study of Middle Atlas (Morocco) peridotite xenoliths: Evidence for coupled introduction of metasomatic sulphides and clinopyroxene

We present major element and PGE (platinum-group-element) abundances in addition to Re–Os isotope data for 11 spinel-facies whole rock peridotites from a single maar from the Middle Atlas Mountains, Morocco.Major element systematics of these xenoliths are generally correlated with indices of depletion. FeO–MgO systematics appear to suggest spinel-facies melting in the range of 5 to 25%. However, Al₂O₃ abundances in these xenoliths appear elevated relative to primitive mantle (Prima). The Al₂O₃ abundances in conjunction with other major elements require distinct re-enrichment of the Middle Atlas continental mantle root due to melt/rock reaction and precipitation of amphibole and/or clinopyroxene from passing silicate melts akin to MORB or OIB that evolved in reverse direction along the melting curves in e.g. FeO–MgO space. Sc and V confirm the range of apparent depletion and also indicate that the currently preserved fO₂ in these peridotites is distinctly different from fO₂ conditions observed in subduction zones.The majority of these xenoliths have low Os and Ir (I-PGEs) concentrations relative to Prima and modelled sulphide- and clinopyroxene-depleted residues of mantle melting under low fO₂, mid-ocean ridge-like conditions. Moreover, Pt and Pd (P-PGE) abundances are elevated when compared to their expected abundances after substantial melt extraction. Importantly, the systematically low Ir abundances in the majority of samples show well-correlated trends with Al₂O₃, MgO and Cu that are inconsistent with established melting trends. Os isotopes in the Middle Atlas xenoliths range from ¹⁸⁷Os/¹⁸⁸Os = 0.11604 to 0.12664 although most samples are close to chondritic. The Os isotope ratios are decoupled from ¹⁸⁷Re/¹⁸⁸Os but, together with Re abundances, also exhibit a good correlation with Al₂O₃, MgO and Cu.The major element, I-PGE and Os isotope correlations suggest that the initial melt depletion led to the exhaustion of sulphide and clinopyroxene (20 to 30%) without significant stabilization of I-PGE-rich alloys. During later modal metasomatism of the refractory Middle Atlas continental mantle root with silicate melts akin to MORB or OIB the introduction of clinopyroxene/amphibole reduced the volume of the melt inducing sulphur saturation in these melts causing precipitation of secondary sulphides. This coupled crystallization of pyroxenes and sulphides (chalcopyrite) resulted in the two-component mixing systematics exhibited by I-PGEs, Os isotopes with major elements and Cu preserved in the Middle Atlas continental mantle root.     

Oxygen and bulk element abundances in Luna 20 fines

Abundances of O, Si, Al and Mn have been determined in Luna 20 fines sample 22001,9 by instrumental neutron activation analysis. The abundances of O, Si and Al are among the highest we have observed in lunar samples and reflect a highlands origin for much of this regolith sample. The Luna 20 abundances reported here most closely resemble those we have determined in four samples of two Apollo 16 fines, rock 14310, and a clast from breccia 15459. The Luna 20 $\text{O}\text{Si}$ ratio of 1.96 ± 0.05 is similar to that in most other lunar samples, but the $\text{Al}\text{Si}$ ratio of 0.532 ± 0.024 is exceeded only by our data on the Apollo 16 fines. This $\text{Al}\text{Si}$ ratio is in agreement with the value of 0.55 ± 0.06 determined by the remote X-ray fluorescence experiment for the highlands between Mare Crisium and Mare Smythii which lie near the Luna 20 site (Adleret al., 1972).     

Meteoritic material at four Canadian impact craters

Eleven impact melt and 6 basement rock samples from 4 craters were analyzed by neutron activation for Au, Co, Cr, Fe, Ge, Ir, Ni, Os, Pd, Re and Se. Wanapitei Lake, Ontario: the impact melts show uniform enrichments corresponding to 1–2% C1-chondrite material. Interelement ratios ($\text{Co}\text{Cr}$, $\text{Ni}\text{Cr}$, $\text{Ni}\text{Ir}$) suggest that the impacting body was a Cl-, C2-, or LL-chondrite. Nicholson Lake, North West Territory: Ni, Cr and Co are distinctly more enriched than Ir and Au which tentatively suggests an olivine-rich achondrite (nakhlite or ureilite). Gow Lake, Saskatchewan and Mistastin, Labrador: small enrichments in Ir and Ni; both the low $\text{Ir}\text{Ni}$ ratios and low Cr content suggest iron meteorites, but the signals are too weak for conclusive identification.A tentative comparison of meteoritic signatures at 10 large, ≥4km craters and their presumed celestial counterparts (13 Apollo and Amor asteroids) shows more irons and achondrites among known projectile types, and a preponderance of S-type objects, having no known meteoritic equivalent, among asteroids. It is not yet clear that these differences are significant, in view of the tentative nature of the crater identifications (achondrites in particular), and the limited statistics.     

Highly siderophile element composition of the Earth’s primitive upper mantle: Constraints from new data on peridotite massifs and xenoliths

Osmium, Ru, Ir, Pt, Pd and Re abundances and ¹⁸⁷Os/¹⁸⁸Os data on peridotites were determined using improved analytical techniques in order to precisely constrain the highly siderophile element (HSE) composition of fertile lherzolites and to provide an updated estimate of HSE composition of the primitive upper mantle (PUM). The new data are used to better constrain the origin of the HSE excess in Earth’s mantle. Samples include lherzolite and harzburgite xenoliths from Archean and post-Archean continental lithosphere, peridotites from ultramafic massifs, ophiolites and other samples of oceanic mantle such as abyssal peridotites. Osmium, Ru and Ir abundances in the peridotite data set do not correlate with moderately incompatible melt extraction indicators such as Al₂O₃. Os/Ir is chondritic in most samples, while Ru/Ir, with few exceptions, is ca. 30% higher than in chondrites. Both ratios are constant over a wide range of Al₂O₃ contents, but show stronger scatter in depleted harzburgites. Platinum, Pd and Re abundances, their ratios with Ir, Os and Ru, and the ¹⁸⁷Os/¹⁸⁸Os ratio (a proxy for Re/Os) show positive correlations with Al₂O₃, indicating incompatible behavior of Pt, Pd and Re during mantle melting. The empirical sequence of peridotite-melt partition coefficients of Re, Pd and Pt as derived from peridotites () is consistent with previous data on natural samples. Some harzburgites and depleted lherzolites have been affected by secondary igneous processes such as silicate melt percolation, as indicated by U-shaped patterns of incompatible HSE, high ¹⁸⁷Os/¹⁸⁸Os, and scatter off the correlations defined by incompatible HSE and Al₂O₃. The bulk rock HSE content, chondritic Os/Ir, and chondritic to subchondritic Pt/Ir, Re/Os, Pt/Re and Re/Pd of many lherzolites of the present study are consistent with depletion by melting, and possibly solid state mixing processes in the convecting mantle, involving recycled oceanic lithosphere. Based on fertile lherzolite compositions, we infer that PUM is characterized by a mean Ir abundance of 3.5 ± 0.4 ng/g (or 0.0080 ± 0.0009*CI chondrites), chondritic ratios involving Os, Ir, Pt and Re (Os/Ir_PUM of 1.12 ± 0.09, Pt/Ir_PUM = 2.21 ± 0.21, Re/Os_PUM = 0.090 ± 0.002) and suprachondritic ratios involving Ru and Pd (Ru/Ir_PUM = 2.03 ± 0.12, Pd/Ir_PUM = 2.06 ± 0.31, uncertainties 1σ). The combination of chondritic and modestly suprachondritic HSE ratios of PUM cannot be explained by any single planetary fractionation process. Comparison with HSE patterns of chondrites shows that no known chondrite group perfectly matches the PUM composition. Similar HSE patterns, however, were found in Apollo 17 impact melt rocks from the Serenitatis impact basin [Norman M.D., Bennett V.C., Ryder G., 2002. Targeting the impactors: siderophile element signatures of lunar impact melts from Serenitatis. Earth Planet. Sci. Lett, 217-228.], which represent mixtures of chondritic material, and a component that may be either of meteoritic or indigenous origin. The similarities between the HSE composition of PUM and the bulk composition of lunar breccias establish a connection between the late accretion history of the lunar surface and the HSE composition of the Earth’s mantle. Although late accretion following core formation is still the most viable explanation for the HSE abundances in the Earth’s mantle, the “late veneer” hypothesis may require some modification in light of the unique PUM composition.     

Isotopic and incompatible element constraints on the genesis of island arc volcanics from Cold Bay and Amak Island,Aleutians, and implications for mantle structure

Cold Bay and Amak Island, two Quaternary volcanic centers in the eastern Aleutians, are orthogonal relative to the trench and separated by ~50 km. Sr, Nd and Pb isotopic compositions of the calc-alkaline andesite magmas show no sign of contamination from continental crust (average ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.70323}$, ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{= 0.51301}$, ${}^{206}\text{Pb}{}^{204}\text{Pb}\text{= 18.82}$, ${}^{207}\text{Pb}{}^{204}\text{Pb}\text{= 15.571}$). These samples plot within the mantle arrays for Sr-Nd and for Pb and are similar to arcs such as the Marianas and New Britain (Sr-Nd) and Marianas and Tonga (Pb). Incompatible element ratios for the Aleutian andesites (K/Rb ~ 332, K/Cs ~ 10,600, K/Sr ~ 22.4, K/Ba ~ 18.3, Ba/La ~ 60) are within the range reported for arc basalts, despite the difference in degree of fractionation.Average K content, K/Rb, K/Ba and K/Sr are approximately the same for basalts from arcs and from oceanic islands (OIB); K/Cs is a factor of 4 lower and Ba/La almost 3 times higher in arcs. Abundance ratio correlations indicate that arcs are enriched in Cs and depleted in La relative to OIB, with other incompatible element abundances very similar. Histograms of Sr and Nd isotopic compositions for MORB, OIB, and intraoceanic arcs show remarkably similar peaks and distribution patterns for intraoceanic arcs and OIB.A “plum pudding” model for the upper mantle best accommodates a) geochemical coherence of OIB and IAV, b) the existence of mantle plumes at some oceanic islands, and c) the presence of a MORB-type source at back arc spreading centers. In this model, OIB plums are imbedded in a MORB matrix; small degrees of melting generate OIB-type magmas while larger degrees of melting dilute the OIB magma with MORB matrix melts.OIB plums are merely less robust lower mantle plumes (i.e., blobs) which are distributed throughout the upper mantle by convection. The existence of at least two types of OIB, as indicated by Sr, Nd, and Pb isotopes, suggests that nuggets of recycled oceanic lithosphère may coexist with lower-mantle plums and that both may be tapped in arcs and intraplate environments.     

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.     

Chalcophile element partitioning between sulfide phases and hydrous mantle melt: Applications to mantle melting and the formation of ore deposits

Understanding the geochemical behavior of chalcophile elements in magmatic processes is hindered by the limited partition coefficients between sulfide phases and silicate melt, in particular at conditions relevant to partial melting of the hydrated, metasomatized upper mantle. In this study, the partitioning of elements Co, Ni, Cu, Zn, As, Mo, Ag, and Pb between sulfide liquid, monosulfide solid solution (MSS), and hydrous mantle melt has been investigated at 1200 °C/1.5 GPa and oxygen fugacity ranging from FMQ−2 to FMQ+1 in a piston-cylinder apparatus. The determined partition coefficients between sulfide liquid and hydrous mantle melt are: 750–1500 for Cu; 600–1200 for Ni; 35–42 for Co; 35–53 for Pb; and 1–2 for Zn, As, and Mo. The partition coefficients between MSS and hydrous mantle melt are: 380–500 for Cu; 520–750 for Ni; ∼50 for Co; <0.5 for Zn; 0.3–6 for Pb; 0.1–2 for As; 1–2 for Mo; and >34 for Ag. The variation of the data is primarily due to differences in oxygen fugacity. These partitioning data in conjunction with previous data are applied to partial melting of the upper mantle and the formation of magmatic-hydrothermal Cu–Au deposits and magmatic sulfide deposits.I show that the metasomatized arc mantle may no longer contain sulfide after >10–14% melt extraction but is still capable of producing the Cu concentrations in the primitive arc basalts, and that the comparable Cu concentrations in primitive arc basalts and in MORB do not necessarily imply similar oxidation states in their source regions.Previous models proposed for producing Cu- and/or Au-rich magmas have been reassessed, with the conclusions summarized as follows. (1) Partial melting of the oxidized (fO₂ > FMQ), metasomatized arc mantle with sulfide exhaustion at degrees >10–14% may not generate Cu-rich, primitive arc basalts. (2) Partial melting of sulfide-bearing cumulates in the root of thickened lower continental crust or lithospheric mantle does not typically generate Cu- and/or Au-rich magmas, but they do have equivalent potential as normal arc magmas in forming magmatic-hydrothermal Cu–Au deposits in terms of their Cu–Au contents. (3) It is not clear whether partial melting of subducting metabasalts generates Cu-rich adakitic magmas, however adakitic magmas may extract Cu and Au via interaction with mantle peridotite. Furthermore, partial melting of sulfide-bearing cumulates in the deep oceanic crust may be able to generate Cu- and Au-rich magmas. (4) The stabilization of MSS during partial melting may explain the genetic link between Au-Cu mineralization and the metasomatized lithospheric mantle.The chalcophile element tonnage, ratio, and distribution in magmatic sulfide deposits depend on a series of factors. This study reveals that oxygen fugacity also plays an important role in controlling Cu and Ni tonnage and Cu/Ni ratio in magmatic sulfide deposits. Cobalt, Zn, As, Sn, Sb, Mo, Ag, Pb, and Bi concentrations and their ratios in sulfide, due to their different partitioning behavior between sulfide liquid and MSS, can be useful indices for the distribution of platinum-group elements and Au in magmatic sulfide deposits.     

Trace elements and Sr-isotopes in some mantle-derived hydrous minerals and their significance

New analyses of K, Rb, Sr and Ba contents and the ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of eight amphiboles, one phlogopite, two diopsides and one host alkalic basalt for an amphibole are reported: The samples are mostly inclusions in alkalic basalts and occur in association with peridotite inclusions. Two of the samples are from alpine-type peridotite bodies — one from the Etang de Lhers massif in the French Pyrenees and the other from the Finero massif in the Ivrea zone in northern Italy. The kaersutites come from the following localities: Hoover Dam, Arizona; Deadman Lake, California; Massif Central, France; Queensland; Spring Mountain, New South Wales.The data indicate that kaersutitic amphiboles are genetically unrelated to their host basalts. The isotopic and trace element data of these amphiboles further strengthens the suggestion of BASU and MURTHY (1977) that kaersutites play a significant role in ocean ridge basalt genesis. In addition, pargasitic amphibole with higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios, if present, may be important in the source regions of alkalic basalts.The bulk amphibole lherzolite from Lherz has the $\text{K}\text{Rb}$ratio and ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio appropriate for source material of ridge tholeiites. If the diopside and the amphibole in this rock had isotopically equilibrated under upper mantle conditions, the data show the time of last equilibration to be approximately 735 m.y., in contrast to the young emplacement age of the ultramafic massif.The coexisting phlogopite and diopside in the spinel lherzolite inclusion from Kilbourne Hole, New Mexico, show, surprisingly, isotopic equilibration under upper mantle conditions despite their drastically different $\text{Rb}\text{Sr}$ ratios. The data show that the phlogopite must have formed very recently in the upper mantle. This phlogopite also has a high $\text{K}\text{Rb}$ ratio (1133), contrary to the commonly held view that mantle phlogopites have low $\text{K}\text{Rb}$ ratios. The coexisting diopside shows high K content (778 ppm) and a lower $\text{K}\text{Rb}$ ratio than the phlogopite. This phlogopite lherzolite has trace elemental and isotopic characteristics that may be adequate for the origin of alkalic basalts upon partial melting.     

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.     

Deccan traps mantle degassing in the terminal Cretaceous marine extinctions

Mantle degassing continually releases gases onto the earth's surface. Over geologically long time intervals, a general equilibrium probably exists between mantle CO₂ release and uptake by surficial sinks. However, during periods of rapid plate movement, or continental flood basalt volcanism, the increased rate of mantle CO₂ release may exceed that of uptake, leading to CO₂ accumulation in the atmosphere and the marine mixed layer (top 50–100 m). This in turn triggers chemical changes in the mixed layer, climatic warming, and bioevolutionary turnover. The Cretaceous/Tertiary ($\text{K}\text{T}$) transition at 65 Ma seems to have been a time of major mantle degassing which induced a perturbation of the carbon cycle. During the $\text{K}\text{T}$ transition, Deccan Traps volcanism, perhaps the greatest episode of continental flood basalt volcanism in the Phanerozoic, flooded an estimated 2.6 × 10⁶ km² of India with basaltic lavas, releasing 5 × 10¹⁷ moles of CO₂ into the earth's atmosphere over a duration 0.53–1.36 Ma at the rate of 3.9 × 10¹¹ to 9.6 × 10¹¹ moles CO₂ per year. The modern mean annual rate of mantle CO₂ release from all sources is 4.1 × 10¹² moles CO₂ per year; assuming a comparable rate of release prior to the Deccan Traps volcanism, the Deccan Traps addition would have elevated the rate of mantle CO₂ release by 10–25%. Sluggish marine circulation and warm, deep, oceans (14–15°C) would have exacerbated CO₂ buildup in the atmosphere, accounting for the Cretaceous to Tertiary drop in oxygen-18 via climatic warming, and, in the marine mixed layer (top 50–100 m), explaining the selective nature of the terminal Cretaceous marine extinctions via a pH change. The extinctions were most severe amongst the calcareous microplankton of the mixed layer; calcareous microplankton (planktonic foraminifera and coccolithophorids) begin to have pH problems at 7.8 and 7.5, respectively. Failure of the coccolithophorids would have disrupted the Williams-Riley pump (algal productivity-gravity pump of CO₂ from the atmosphere and mixed layer into the deep oceans) producing dead ocean conditions (severely reduced photosynthesis and CaCO₃ production). Failure of the Williams-Riley pump is reflected in the extinctions themselves, and in the loss of biogenic CaCO₃ to the sea floor, causing the $\text{K}\text{T}$ boundary hiatus and (or) the $\text{K}\text{T}$ boundary clay. Failure of the pump today would elevate atmospheric pCO₂ severalfold; the $\text{K}\text{T}$ failure would have responded comparably. Dead ocean conditions would, in themselves, have produced a major CO₂ buildup. Early Tertiary “Strangelove” conditions in the mixed layer, characterized by a dominance of the thoracosphaerids, braarudosphaerids and small planktonic foraminifera, were coeval with the main pulse of Deccan Traps volcanism. Overall, the record is one of gradual $\text{K}\text{T}$ bioevolutionary turnover during a period of disequilibrium between the rate of mantle CO₂ degassing and uptake by sinks. Mantle degassing during the Deccan Traps volcanism unifies the $\text{K}\text{T}$ biological and physicochemical records.