Fluorine and chlorine in mantle minerals and the halogen budget of the Earth’s mantle

The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth’s upper mantle and their distribution in peridotite minerals remain to be constrained. Here, we developed a method to measure low concentrations of halogens (≥0.4 µg/g F and ≥0.3 µg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in co-existing natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (<1 µg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 µg/g F and 0.14–0.38 µg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 µg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.     

Trace-element characteristics of east–west mantle geochemical hemispheres

Recent statistical analyses on the isotopic compositions of oceanic, arc, and continental basalts have revealed that the Earth's mantle is broadly divided into eastern and western hemispheres. The present study aimed to characterize the isotopically defined east–west geochemical hemispheres using trace-element concentrations. Basalt data with Rb, Sr, Nd, Sm, Pb, Th, and U in addition to the isotopic ratios ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb were selected mostly from the GEOROC and PetDB databases. A total of 4787 samples were used to investigate the global geochemical variations. The results show that the wide trace-element variations are broadly explained by the melting of melt-metasomatized and fluid-metasomatized mantle sources. The larger amount of the fluid component derived from subducted plates in the eastern hemisphere than that in the western hemisphere is inferred from the basalts. These characteristics support the hypothesis that focused subduction towards the supercontinent created the mantle geochemical hemispheres.     

Evolution and composition of the lithospheric mantle underneath the western Arabian peninsula: constraints from Sr−Nd isotope systematics of mantle xenoliths

On the basis of their textures and mineral compositions spinel-peridotite xenoliths of the Cr-diopside group (group I) from Cenozoic volcanic fields of Arabia can be classified into different subtypes. Type IA is of lherzolitic to harzburgitic composition; mineral compositions are similar to those of group I mantle xenoliths from worldwide occurrences. Type IB xenoliths have lherzolitic to wehrlitic compositions; Mg/(Mg+Fe) ratios of the clinopyroxenes (0.862–0.916) and olivines (0.872–0.914) are similar too or slightly lower than those of typical IA minerals. Texturally, type IB xenoliths are distinguished from type IA rocks by the presence of intragranular spinel, intragranular relict Cr-pargasite, and subordinate intergranular Ba-phlogopite (11.1% BaO). The hydrous minerals in type IB xenoliths are interpreted to document an earlier metasomatism 1 which did not affect type IA lithospheric mantle. Subsequent recrystallization caused the partial replacement of Cr-pargasite in type IB materials and resulted in the formation of less hydrous mineral assemblages. Some of the type IA xenoliths are characterized by secondary intergranular amphibole which must have formed recently. The absence or presence of this intergranular amphibole is used to distinguish an anhydrous subtype IA1 from a hydrous subtype IA2. Type IB xenoliths may also contain secondary intergranular amphibole (similar to the one in subtype IA2) or they contain abundant formermelt patches now consisting of glass and phenocrysts of olivine, clinopyroxene, amphibole, and spinel. The secondary intergranular amphiboles and the former melt patches, both are interpreted as results of a second metasomatism (metasomatism 2). In their trace element and isotopic characteristics, type IA1 and type IA2 clinopyroxenes do not exhibit any systematic differences. Furthermore, type IA2 clinopyroxenes are in Sr isotopic disequilibrium with intergranular amphiboles. This suggests that type IA2 clinopyroxenes were not modified during the second metasomatism 2. All type IA clinopyroxenes have low Sr contents (100 ppm); most of them show Sm/Nd ratios higher than inferred for bulk earth. In their ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios, type IA clinopyroxenes exhibit a large spread from 0.70226–0.70376 and from 0.51375–0.51251, respectively. Highly variable Sr/Nd ratios (5.0–79.3) and variable T_UR and T_CHUR model age relationships require different evolutions of the respective mantle portions. Nevertheless, all but two type IA clinopyroxenes form a linear array in a Sm–Nd isochron diagram which probably can not be explained by mixing. If taken as an isochron the slope of the array corresponds to an age of around 700 Ma. The mean initial _Nd of 5.8±1.7 (1) is similar to values for juvenile Pan-African (i.e. 850–650 Ma old) crust of the Arabian-Nubian shield. It is suggested that type IA lithospheric mantle and the juvenile Pan-African crust are two counterparts fractionated from a common source during the earlier stages of the Pan-African. Type IB clinopyroxenes have high Sr contents (200 ppm), variable Sr/Nd ratios (9–111) and Sm/Nd ratios generally below that inferred for bulk earth, and show a small spread in their Sr and Nd isotopic compositions (0.70299–0.70318 and 0.51285–0.51278, respectively). In a Sm–Nd isochron diagram the data points form a linear, horizontal array indicating a close-to-zero age for the earlier metasomatism 1 and suggesting a close genetic relationship to mantle processes related to the formation of the Red Sea.     

Equation of state of magnesite for the conditions of the Earth’s lower mantle

A semiempirical equation of state was derived for magnesite under the thermodynamic conditions of the Earth’s mantle. Within experimental uncertainties, it is consistent with thermochemical, ultrasonic, X-ray, and shock-wave data at temperatures from 15 K to the melting point and pressures of up to 100–130 GPa. The following values were recommended for the isothermal bulk modulus and its pressure derivative: K _T = 111.71 GPa and K′ = 4.08. Thermodynamic analysis showed that magnesite does not decompose to periclase and CO₂ under the thermodynamic conditions of the Earth’s lower mantle and outer core.     

Hydration and dehydration in the lower margin of a cold mantle wedge: implications for crust–mantle interactions and petrogeneses of arc magmas

Garnet orthopyroxenites from Maowu (Dabieshan orogen, eastern China) were formed from a refractory harzburgite/dunite protolith. They preserve mineralogical and geochemical evidence of hydration/metasomatism and dehydration at the lower edge of a cold mantle wedge. Abundant polyphase inclusions in the cores of garnet porphyroblasts record the earliest metamorphism and metasomatism in garnet orthopyroxenites. They are mainly composed of pargasitic amphibole, gedrite, chlorite, talc, phlogopite, and Cl-apatite, with minor anhydrous minerals such as orthopyroxene, sapphirine, spinel, and rutile. Most of these phases have high X_Mg, NiO, and Ni/Mg values, implying that they probably inherited the chemistry of pre-existing olivine. Trace element analyses indicate that polyphase inclusions are enriched in large ion lithophile elements (LILE), light rare earth elements (LREE), and high field strength elements (HFSE), with spikes of Ba, Pb, U, and high U/Th. Based on the P–T conditions of formation for the polyphase inclusions (?1.4 GPa, 720–850°C), we suggest that the protolith likely underwent significant hydration/metasomatism by slab-derived fluid under shallow–wet–cold mantle wedge corner conditions beneath the forearc. When the hydrated rocks were subducted into a deep–cold mantle wedge zone and underwent high-pressure–ultrahigh-pressure (HP–UHP) metamorphism, amphibole, talc, and chlorite dehydrated and garnet, orthopyroxene, Ti-chondrodite, and Ti-clinohumite formed during prograde metamorphism. The majority of LILE (e.g. Ba, U, Pb, Sr, and Th) and LREE were released into the fluid formed by dehydration reactions, whereas HFSE (e.g. Ti, Nb, and Ta) remained in the cold mantle wedge lower margin. Such fluid resembling the trace element characteristics of arc magmas evidently migrates into the overlying, internal, hotter part of the mantle wedge, thus resulting in a high degree of partial melting and the formation of arc magmas.     

Time series analysis of mantle cycles Part Ⅱ:The geologic record in zircons,large igneous provinces and mantle lithosphere

Igneous and detrital zircons have six major U/Pb isotopic age peaks in common(2700 Ma,1875 Ma.1045 Ma,625 Ma,265 Ma and 90 Ma).For igneous rocks,each age peak is comprised of subpeaks with distinct geographic distributions and a subpeak age range per age peak ≤100 Myr.There are eight major LIP age peaks(found on≥10 crustal provinces)of which only four are in common to major detrital zircon age peaks(2715 Ma,1875 Ma,825 Ma,90 Ma).Of the whole-rock Re depletion ages,58% have correspo nding detrital zircon age peaks and 55% have corresponding LIP age peaks.Ten age pea ks are fou nd in common to igneous zircon,detrital zircon,LIP,and Re depletion age time series(3225 Ma,2875 Ma,2145 Ma,2085 Ma,1985 Ma,1785 Ma,1455 Ma,1175 Ma,825 Ma,and 90 Ma).and these are very robust peaks on a global scale as recorded in both crustal and mantle rocks.About 50% of the age peaks in each of these time series correspond to predicted peaks in a 94-Myr mantle cycle,including four of the ten peaks in common to all four time series(2875 Ma,1785 Ma,825 Ma and 90 Ma).Age peak widths and subpeak ranges per age peak suggest that mantle events responsible for age peaks are100 Myr and many50 Myr in duration.Age peak geographic distributions show three populations(≤1000 Ma,2500-1000 Ma,2500 Ma),with the number of new provinces in which age peaks are represented decreasing with time within each population.The breaks between the populations(at 2.5 Ga and 1 Ga)fall near the onsets of two transitions in Earth history.The First Transition may represent a change from stagnant-lid tectonics into plate tectonics and the Second Transition,the onset of subduction of continental crust.The major factor controlling geographic distribution of age peaks is the changing locations of orogeny.Before ～2 Ga,age subpeaks and peaks are housed in orogens within or around the edges of crustal provinces,mostly in accretionary orogens.but beginning at 1.9 Ga,collisional orogens become more important.The coincidence in duration between magmatic flare-ups in Phanerozoic arcs and duration of age subpeaks(10-30 Myr)is consiste nt with subpeaks representing periods of enhanced arcrelated magmatism.probably caused by increased subduction flux.The correlation of isotopic age peaks between time series supports a cause and effect relationship between mantle plume activity,continental magma production at convergent margins,and crustal deformation.Correlation of over half of the detrital zircon age peaks(and six of the nine major peaks)with Re depletion age peaks supports an interpretation of the zircon peaks as crustal growth rather than selective preservation peaks.     

A brief review of isotopically light Li – a feature of the enriched mantle?

Lithium isotope geochemistry is increasingly being used to trace deep-earth processes, reflecting the observed large variation of Li isotope ratios in mantle-derived rocks, including peridotite xenoliths associated with ancient continents. We briefly review the Li isotopic compositions of major geochemical reservoirs, the assumed mechanisms of Li isotopic fractionation, and, in particular, the origins of isotopically light Li in mantle-derived rocks based on the latest developments in Li isotope geochemistry. Comparison of Li isotope data with existing Sr-Nd isotope ratios reflects the subduction-recycling of ancient oceanic crust and the reappearance of Li in volcanic rocks. This circulation may play an important role in generating the isotopically light-Li component in the mantle – perhaps the enriched mantle end member defined by the Sr-Nd isotopic compositions of oceanic basalts.     

Possible contribution of lower mantle magnesiowüstite metallization into geomagnetic data

Phase change of dielectric magnesiowüstite in the lower mantle may leave signatures in geomagnetic records of the globally distributed array of observatories. We investigate theoretically which may be the contribution of magnesiowüstite metallization to geomagnetic data and how the variations of magnetic susceptibility associated with this phase change may influence the Earth's field. The modeling is performed using spherical harmonic analysis (SHA) of mantle electromagnetic (EM) responses in observatory geomagnetic data at periods of decades, 11 years, 1 year, and 27 days. The existence of a lower mantle conductor is checked against monthly means of real observatory records from 1920 through 2009 obtained by preliminary processing.     

Trace element modeling of aqueous fluid – peridotite interaction in the mantle wedge of subduction zones

Recently measured partition coefficients for Rb, Th, U, Nb, La (Ce), Pb, Sr, Sm, Zr, and Y between lherzolite assemblage minerals and H₂O-rich fluid (Ayers et al. 1997; Brenan et al. 1995a,b) are used in a two-component local equilibrium model to assess the effects of interaction between slab-derived aqueous fluids and wedge lherzolite on the trace element and isotopic composition of island arc basalts (IAB). The model includes four steps representing chemical processes, with each process represented by one equation with one adjustable parameter, in which aqueous fluid: (1) separates from eclogite in the subducted slab (Rayleigh distillation, mass fraction of fluid released F  ^fluid); (2) ascends through the mantle wedge in isolated packets, exchanging elements and isotopes with depleted lherzolite (zone refining, the rock/fluid mass ratio n); (3) mixes with depleted lherzolite (physical mixing, the mass fraction of fluid in the mixture X  ^fluid); (4) induces melting to form primitive IAB (batch melting, mass fraction of melt F ^melt). The amount of mantle lherzolite processed by the fluid in step (2) determines its isotopic and trace element signature and the relative contributions of slab and wedge to primitive IAB. Assuming an average depleted lherzolite composition and mineralogy (70% olivine, 26% orthopyroxene, 3% clinopyroxene and 1% ilmenite) and using nonlinear regression to adjust parameter values to obtain an optimal fit to the average composition of IAB (McCulloch and Gamble 1991) yields values of F  ^fluid= 0.20, n= 26, X  ^fluid= 0.17, and F  ^melt= 0.15, with r  ²= 0.995 and the average relative error in trace element concentration = 6%. The average composition of IAB can also effectively be modeled with no contribution from the slab other than H₂O (i.e., skip model step 1): n= 27, X  ^fluid= 0.21, F  ^melt= 0.17, with r  ²= 0.992. By the time the fluid reaches the IAB source, exchange with depleted wedge lherzolite reduces the ⁸⁷Sr/⁸⁶Sr ratio isotopic composition to near-mantle values and the slab contribution to <50% for all but the most incompatible elements (e.g., Pb). The IAB may retain the slab signature for elements such as B and Be that are highly incompatible and that have very low concentrations in the depleted mantle wedge. The relatively high equilibrium D  ^{mineral /   fluid} values measured by Ayers et al. (1997), Brenan et al. (1995a) and Stalder et al. (1998) suggest that large amounts of fluid (>5 wt%) must be added to lherzolite in the IAB source. Decreasing X  ^fluid below 0.05 causes model results to have unacceptably high levels of error and petrologically unreasonable values of F  ^melt. That H₂O contents of IAB are generally <6 wt% suggests that not all of the H₂O that metasomatizes the IAB source remains in the source to dissolve in the subsequently formed melt. Modeling of the compositions of specific primitive IAB from oceanic settings with low sediment input and depleted mantle wedges (Tonga, Marianas) shows a generally lower level of fluid-wedge interaction (low n), and therefore a larger slab component in primitive IAB. Received: 6 October 1997 / Accepted: 8 May 1998     

Mineralogy of the lower mantle: A review of ‘super-deep’ mineral inclusions in diamond

Starting from the late 1980s, several groups of lower-mantle mineral inclusions in diamond have been found. Three associations were established among them: juvenile ultramafic, analogous to eclogitic, and carbonatitic. The juvenile ultramafic association strongly predominates, and it is composed of ferropericlase, MgSi-, CaSi- and CaTi-perovskites, stishovite, tetragonal almandine-pyrope phase (TAPP), and some others. The association analogous to the upper-mantle eclogitic association, formed from subducting lithosphere, comprises: majorite, CaSi-perovskite bearing compositional Eu anomalies, phase ‘Egg’ with a tetragonal structure, and stishovite. The carbonatitic association is represented by various carbonates, halides, and associated minerals. Some mineral associations (wüstite + periclase and native iron + iron carbides) are, possibly, related to the D″ layer at the core/mantle boundary. The mineralogical composition of the lower mantle is now understood to be more complex than had been suggested in theoretic and experimental works. The proportion of ferropericlase in the lower mantle is higher than it was suggested before, and its composition is more iron-rich (mg = 0.36–0.90) as compared to experimental and theoretical data. Free silica (stishovite) is always present in lower-mantle associations, and a separate aluminous phase (TAPP) has been identified in several areas. These discrepancies suggest that the composition of the lower mantle differs to that of the upper-mantle, and experiments based solely on ‘pyrolitic’ compositions are not, therefore, applicable to the lower mantle. These data indicate a probability of an alternative to the CI-chondrite model of the Earth's formation, for example, an enstatite-chondrite model.     

Experimental characterization of diamond crystallization in melts of mantle silicate-carbonate-carbon systems at 7.0–8.5 GPa

Diamond crystallization from carbon solutions in compositionally variable melts of model eclogite with dolomite [CaMg(CO₃)₂], potassium carbonate (K₂CO₃), and multicomponent K-Na-Ca-Mg-Fe carbonates was studied at 7.0–8.5 GPa. Concentration barriers for the nucleation of the diamond were determined at a standard pressure of 8.5 GPa for variable proportions of silicate and carbonate components in the growth solutions. They correspond to 35, 65, and 40 wt % of silicate components for systems with dolomite, K₂CO₃, and carbonatites, respectively. At higher contents of silicates in silicate-carbonate melts, the nucleation of diamond phase ceases, but diamond crystallization on seed crystals continues and is accompanied by the spontaneous crystallization of thermodynamically unstable graphite. In melts of the albite (NaAlSi₃O₈)-K₂CO₃-C compositions, the concentration barrier of diamond nucleation at 8.5 GPa is up to 90–92 wt % of the albite component, and diamond growth on seeds was observed in albite-carbon melts. Using mineralogical and experimental data, we developed a model of mantle carbonate-silicate (carbonatite) melts as the main parental media for natural diamonds; it was shown that the composition of the silicate constituent of such parental melts is variable and corresponds to the mantle ultrabasic-basic series. With respect to concentration contributions and dominant role in the genesis of diamond in the Earth’s mantle, major (carbonate and silicate) and minor or admixture components were distinguished. The latter include both soluble in carbonate-silicate melts (oxides, phosphates, chlorides, carbon dioxide, and water) and insoluble components (sulfides, metals, and carbides). Both major and minor components may affect the position of the concentration barriers of diamond nucleation in natural parent media.     

Persistence of mantle lithospheric Re–Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (Southern Spain)

The western part of the Ronda peridotite massif (Southern Spain) consists mainly of highly foliated spinel-peridotite tectonites and undeformed granular peridotites that are separated by a recrystallization front. The spinel tectonites are interpreted as volumes of ancient subcontinental lithospheric mantle and the granular peridotites as a portion of subcontinental lithospheric mantle that underwent partial melting and pervasive percolation of basaltic melts induced by Cenozoic asthenospheric upwelling. The Re–Os isotopic signature of sulfides from the granular domain and the recrystallization front mostly coincides with that of grains in the spinel tectonites. This indicates that the Re–Os radiometric system in sulfides was highly resistant to partial melting and percolation of melts induced by Cenozoic lithospheric thermal erosion. The Re–Os isotopic systematics of sulfides in the Ronda peridotites thus mostly conserve the geochemical memory of ancient magmatic events in the subcontinental lithospheric mantle. Os model ages record two Proterozoic melting episodes at ~1.6 to 1.8 and 1.2–1.4 Ga, respectively. The emplacement of the massif into the subcontinental lithospheric mantle probably coincided with one of these depletion events. A later metasomatic episode caused the precipitation of a new generation of sulfides at ~0.7 to 0.9 Ga. These Proterozoic Os model ages are consistent with results obtained for several mantle suites in Central/Western Europe and Northern Africa as well as with the Nd model ages of the continental crust of these regions. This suggests that the events recorded in mantle sulfides of the Ronda peridotites reflect different stages of generation of the continental crust in the ancient Gondwana supercontinent.     

Evolution of subcontinental lithospheric mantle beneath eastern China: Re–Os isotopic evidence from mantle xenoliths in Paleozoic kimberlites and Mesozoic basalts

The ages of subcontinental lithospheric mantle beneath the North China and South China cratons are less well-constrained than the overlying crust. We report Re–Os isotope systematics of mantle xenoliths entrained in Paleozoic kimberlites and Mesozoic basalts from eastern China. Peridotite xenoliths from the Fuxian and Mengyin Paleozoic diamondiferous kimberlites in the North China Craton give Archean Re depletion ages of 2.6–3.2 Ga and melt depletion ages of 2.9–3.4 Ga. No obvious differences in Re and Os abundances, Os isotopic ratios and model ages are observed between spinel-facies and garnet-facies peridotites from both kimberlite localities. The Re–Os isotopic data, together with the PGE concentrations, demonstrate that beneath the Archean continental crust of the eastern North China Craton, Archean lithospheric mantle of spinel- to diamond-facies existed without apparent compositional stratification during the Paleozoic. The Mesozoic and Cenozoic basalt-borne peridotite and pyroxenite xenoliths, on the other hand, show geochemical features indicating metasomatic enrichment, along with a large range of the Re–Os isotopic model ages from Proterozoic to Phanerozoic. These features indicate that lithospheric transformation or refertilization through melt-peridotite interaction could be the primary mechanism for compositional changes during the Phanerozoic, rather than delamination or thermal-mechanical erosion, despite the potential of these latter processes to play an important role for the loss of garnet-facies mantle. A fresh garnet lherzolite xenolith from the Yangtze Block has a Re depletion age of ∼1.04 Ga, much younger than overlying Archean crustal rocks but the same Re depletion ages as spinel lherzolite xenoliths from adjacent Mesozoic basalts, indicating Neoproterozoic resetting of the Re–Os system in the South China Craton.