Molybdenum systematics of subducted crust record reactive fluid flow from underlying slab serpentine dehydration.

Fluids liberated from subducting slabs are critical in global geochemical cycles. We investigate the behaviour of Mo during slab dehydration using two suites of exhumed fragments of subducted, oceanic lithosphere. Our samples display a positive correlation of δ98/95MoNIST 3134 with Mo/Ce, from compositions close to typical mantle (-0.2‰ and 0.03, respectively) to very low values of both δ98/95MoNIST 3134 (-1‰) and Mo/Ce (0.002). Together with new, experimental data, we show that molybdenum isotopic fractionation is driven by preference of heavier Mo isotopes for a fluid phase over rutile, the dominant mineral host of Mo in eclogites. Moreover, the strongly perturbed δ98/95MoNIST 3134 and Mo/Ce of our samples requires that they experienced a large flux of oxidised fluid. This is consistent with channelised, reactive fluid flow through the subducted crust, following dehydration of the underlying, serpentinised slab mantle. The high δ98/95MoNIST 3134 of some arc lavas is the complement to this process.

Simple and cost-effective methods for precise analysis of trace element abundances in geological materials with ICP-MS.

Inductively coupled plasma mass spectrometry (ICP-MS) is the most commonly used technique to determine the abundances of trace elements in a wide range of geological materials. However, incomplete sample digestion, isobaric interferences and instrumental drift remain obvious problems that must be overcome in order to obtain precise and accurate results. For this reason, we have done many experiments and developed a set of simple, cost-effective and practical methods widely applicable for precise and rapid determination of trace element abundances in geological materials using ICP-MS. Commonly used high-pressure digestion technique is indeed effective in decomposing refractory phases, but this inevitably produces fluoride complexes that create new problems. We demonstrate that the fluoride complexes formed during high-pressure digestion can be readily re-dissolved using high-pressure vessel at 190°C for only 2h for 50mg sample. In the case of isobaric interferences, although oxide (e.g., MO+/M+) and hydroxide (e.g., MOH+/M+) productivity is variable between runs, the (MO+/M+)/(CeO+/Ce+) and (MOH+/M+)/(CeO+/Ce+) ratios remain constant, making isobaric interference correction for all other elements of interest straightforward, for which we provide an easy-to-use off-line procedure. We also show that mass-time-intensity drift curve is smooth as recognized previously, for which the correction can be readily done by analyzing a quality-control (QC) solution and using off-line Excel VBA procedure without internal standards. With these methods, we can produce data in reasonable agreement with recommended values of international rock reference standards with a relative error of <8% and precision generally better than 5%. Importantly, compared to the widely used analytical practice, we can effectively save >60% of time (e.g., <24h vs. >60h).

Testing the mantle plume hypothesis: an IODP effort to drill into the Kamchatka-Okhotsk Sea basement.

The great mantle plume debate (GPD) has been going on for ∼15years (Foulger and Natland, 2003; Anderson, 2004; Niu, 2005; Davies, 2005; Foulger, 2005; Campbell, 2005; Campbell and Davies, 2006), centered on whether mantle plumes exist as a result of Earth's cooling or whether their existence is purely required for convenience in explaining certain Earth phenomena (Niu, 2005). Despite the mounting evidence that many of the so-called plumes may be localized melting anomalies, the debate is likely to continue. We recognize that the slow progress of the debate results from communication difficulties. Many debaters may not truly appreciate (1) what the mantle plume hypothesis actually is, and (2) none of the petrological, geochemical and geophysical methods widely used can actually provide smoking-gun evidence for or against mantle plume hypothesis. In this short paper, we clarify these issues, and elaborate a geologically effective approach to test the hypothesis. According to the mantle plume hypothesis, a thermal mantle plume must originate from the thermal boundary layer at the core-mantle boundary (CMB), and a large mantle plume head is required to carry the material from the deep mantle to the surface. The plume head product in ocean basins is the oceanic plateau, which is a lithospheric terrane that is large (1000's km across), thick (>200km), shallow (2-4km high above the surrounding seafloors), buoyant (∼1% less dense than the surrounding lithosphere), and thus must be preserved in the surface geology (Niu et al., 2003). The Hawaiian volcanism has been considered as the surface expression of a type mantle plume, but it does not seem to have a (known) plume head product. If this is true, the Hawaiian mantle plume in particular and the mantle plume hypothesis in general must be questioned. Therefore, whether there is an oceanic plateau-like product for the Hawaiian volcanism is key to testing the mantle plume hypothesis, and the Kamchatka-Okhotsk Sea basement is the best candidate to find out if it is indeed the Hawaiian mantle plume head product or not (Niu et al., 2003; Niu, 2004).

Magmatic record of India-Asia collision.

New geochronological and geochemical data on magmatic activity from the India-Asia collision zone enables recognition of a distinct magmatic flare-up event that we ascribe to slab breakoff. This tie-point in the collisional record can be used to back-date to the time of initial impingement of the Indian continent with the Asian margin. Continental arc magmatism in southern Tibet during 80-40 Ma migrated from south to north and then back to south with significant mantle input at 70-43 Ma. A pronounced flare up in magmatic intensity (including ignimbrite and mafic rock) at ca. 52-51 Ma corresponds to a sudden decrease in the India-Asia convergence rate. Geological and geochemical data are consistent with mantle input controlled by slab rollback from ca. 70 Ma and slab breakoff at ca. 53 Ma. We propose that the slowdown of the Indian plate at ca. 51 Ma is largely the consequence of slab breakoff of the subducting Neo-Tethyan oceanic lithosphere, rather than the onset of the India-Asia collision as traditionally interpreted, implying that the initial India-Asia collision commenced earlier, likely at ca. 55 Ma.

The terrestrial uranium isotope cycle.

Changing conditions on the Earth's surface can have a remarkable influence on the composition of its overwhelmingly more massive interior. The global distribution of uranium is a notable example. In early Earth history, the continental crust was enriched in uranium. Yet after the initial rise in atmospheric oxygen, about 2.4 billion years ago, the aqueous mobility of oxidized uranium resulted in its significant transport to the oceans and, ultimately, by means of subduction, back to the mantle. Here we explore the isotopic characteristics of this global uranium cycle. We show that the subducted flux of uranium is isotopically distinct, with high (238)U/(235)U ratios, as a result of alteration processes at the bottom of an oxic ocean. We also find that mid-ocean-ridge basalts (MORBs) have (238)U/(235)U ratios higher than does the bulk Earth, confirming the widespread pollution of the upper mantle with this recycled uranium. Although many ocean island basalts (OIBs) are argued to contain a recycled component, their uranium isotopic compositions do not differ from those of the bulk Earth. Because subducted uranium was probably isotopically unfractionated before full oceanic oxidation, about 600 million years ago, this observation reflects the greater antiquity of OIB sources. Elemental and isotope systematics of uranium in OIBs are strikingly consistent with previous OIB lead model ages, indicating that these mantle reservoirs formed between 2.4 and 1.8 billion years ago. In contrast, the uranium isotopic composition of MORB requires the convective stirring of recycled uranium throughout the upper mantle within the past 600 million years.

Lithium isotope evidence for subduction-enriched mantle in the source of mid-ocean-ridge basalts.

'Recycled' crustal materials, returned from the Earth's surface to the mantle by subduction, have long been invoked to explain compositional heterogeneity in the upper mantle. Yet increasingly, problems have been noted with this model. The debate can be definitively addressed using stable isotope ratios, which should only significantly vary in primitive, mantle-derived materials as a consequence of recycling. Here we present data showing a notable range in lithium isotope ratios in basalts from the East Pacific Rise, which correlate with traditional indices of mantle heterogeneity (for example, 143Nd/144Nd ratios). Such co-variations of stable and radiogenic isotopes in melts from a normal ridge segment provide critical evidence for the importance of recycled material in generating chemical heterogeneity in the upper mantle. Contrary to many models, however, the elevated lithium isotope ratios of the 'enriched' East Pacific Rise lavas imply that subducted ocean crust is not the agent of enrichment. Instead, we suggest that fluid-modified mantle, which is enriched during residency in a subduction zone, is mixed back into the upper mantle to cause compositional variability.

Constraints on melt movement beneath the East Pacific Rise from 230Th-238U disequilibrium.

We report 230Th-238U disequilibrium data on mid-ocean ridge basalts recovered 5 to 40 kilometers off the ridge axis near 9 degrees 30'N of the East Pacific Rise. These data indicate near-symmetrical eruptions of normal mid-ocean ridge basalts (NMORBs) and incompatible element-enriched mid-ocean ridge basalts (EMORBs) as far as 20 kilometers off axis. Our results suggest large-scale subsurface lateral transport of NMORB melt at 19 to 21 centimeters per year and also provide constraints on the petrogenesis of EMORBs of off-axis origin.