Lu-Hf同位素的MC-ICP-MS实验方法及其在华北克拉通典型火山岩研究中的应用

Over past ten years, a great development has been made in the Lu-Hf isotopic system with the advent of MC-ICP-MS. Based on a comprehensive review of available references in the related field, a novel analytical protocol of three exchange chromatographies after one mixed acid attacking geological samples was developed in this work, which not only avoids common multiple sample treatments for natural inhomegeneous samples, but also is useful for Rb-Sr, Sm-Nd and Lu-Hf isotopic system simultaneously, especially for the garnet- and apatite-bearing rocks for the Sm-Nd and Lu-Hf geochronology. An analytical procedure for the Lu and Hf concentration in geological samples determined by by ID-MC-ICP-MS was detailedly investigated. The Hf yield is > 90 % and total procedural blank is less than. 50 pg for Hf and 10 pg for Lu, respectively. The developed method was successfully applied to the determination of Lu and Hf concentrations for USGS geological materials. A one-column procedure for Hf purification in geological samples using common anion exchange chromatography and its isotopic analyses by MC-ICP-MS were also established. Multiple analyses of Standard Reference Materials demonstrate that this method was simple, time-saving, cheap and efficient, especially suitable for the Hf isotopic compositions of young samples. Finally, the measurements of Sr and Nd isotopic compositions using Neptune MC-ICP-MS were described briefly, which indicates that Neptune MC-ICP-MS can precisely measure Sr and Nd isotopic compositions as the TIMS does, even more efficient and less time-consuming than the TIMS method. The Hf isotopic characteristics of typical volcanic rocks (Cenozoic Changle-Linqu basalts, Mesozoic Fangcheng basalts, Mesozoic Jianguo basalts, Mesozoic Wulahada high-Mg andesite, Cenozoic Fanshi, Zuoquan and Xiyang-Pingding basalts of the Taihang Mountains, Paleozoic diamondiferous Menyin and Fuxian Kimblites) from the North China Craton were firstly studied in this work. Coupled with Nd isotopic compositions, it shows that the Hf isotopes could be a better tracer for mantle sources than the Nd isotopes. Individual kimberlite fields from both the Mengyin and Fuxian regions have quite uniform Hf isotopic compositions, similar to the situation for the Nd isotopes.

U-Pb-Hf-trace element systematics and geochronology of zircon from a granulite-facies metamorphosed mafic-ultramafic layered complex in Central Brazil

Zircon recrystallization is a common process during high-grade metamorphism and promotes partial or complete resetting of the original isotopic and chemical characteristics of the mineral and thus complicates U-Pb geochronological interpretation. In Central Brazil, this complexity may be illustrated by three composite mafic-ultramafic intrusions metamorphosed under amphibolite-to-granulite conditions. Their ages of emplacement and metamorphic ages have been a matter of controversy for the last thirty years. The Serra da Malacacheta and Barro Alto complexes make up the southernmost of these layered bodies and four samples from distinct rock types were investigated in order to verify the consequences of metamorphic alteration of zircon for U-Pb dating. Cathodoluminescent imaging reveals internal features which are typical of concomitant dissolution-reprecipitation processes, such as convolute zoning and inward-moving recrystallization fronts, even in samples in which partially preserved igneous textures are observed. Due to this extensive alteration, LA-ICPMS U-Pb isotopic analysis yielded inconclusive data. However, in situ Hf isotopic and trace-element analyses help to clarify the real meaning of the geochronological data. Low Lu/Hf (<0.004) and homogeneous (176)Hf/(177)Hf(t) values imply that the zircon populations within individual samples have crystallized in a single episode, despite the observed variations in age values. Trace element signatures of zircon grains from garnet-bearing samples reveal that they were unreactive to the development of the peak metamorphism mineral assemblage and, thus, the main chemical feature in such grains is attributed to a coupled dissolution-reprecipitation process. However, in the Cafelandia amphibolite an additional alteration process is identified, probably related to the influx of late-stage fluids. Combined isotopic and geochemical investigation on zircon grains allowed the distinction of two magmatic events. The first corresponds to the crystallization of the Serra da Malacacheta Complex and characterizes a juvenile magmatism at similar to 1.3 Ga. The younger episode, recognized in the Barro Alto Complex, is dated at ca. 800 Ma and is represented by mafic and ultramafic rocks showing intense contamination with continental crust, implying that the emplacement took place, most likely, in a continental back-arc setting. Altered zircon domains as well as titanite grains date the metamorphic event at ca. 760-750 Ma. (C) 2011 Elsevier B.V. All rights reserved.

Radiogenic Hf isotopic composition of continental eolian dust in Pacific Ocean sediments

The inorganic silicate fraction extracted from bulk pelagic sediments from the North Pacific Ocean is eolian dust. It monitors the composition of continental crust exposed to erosion in Asia. 176Lu/177Hf ratios of modern dust are subchondritic between 0.011 and 0.016 but slightly elevated with respect to immature sediments. Modern dust samples display a large range in Hf isotopic composition (IC), -4.70 < epsilon-Hf < +16.45, which encompasses that observed for the time series of DSDP cores 885/886 and piston core LL44-GPC3 extending back to the late Cretaceous. Hafnium and neodymium isotopic results are consistent with a dominantly binary mixture of dust contributed from island arc volcanic material and dust from central Asia. The Hf-Nd isotopic correlation for all modern dust samples, epsilon-Hf= =0.78 epsilon-Nd = +5.66 (n =22, R**2 =0.79), is flatter than those reported so far for terrestrial reservoirs. Moreover, the variability in epsilon-Hf of Asian dust exceeds that predicted on the basis of corresponding epsilon-Nd values (34.76 epsilon-Hf < +2.5; -10.96< epsilon-Nd <-10.1). This is attributed to: (1) the fixing of an important unradiogenic fraction of Hf in zircons, balanced by radiogenic Hf that is mobile in the erosional cycle, (2) the elevated Lu/Hf ratio in chemical sediments which, given time, results in a Hf signature that is radiogenic compared with Hf expected from its corresponding Nd isotopic components, and (3) the possibility that diagenetic resetting of marine sediments may incorporate a significant radiogenic Hf component into diagenetically grown minerals such as illite. Together, these processes may explain the variability and more radiogenic character of Hf isotopes when compared to the Nd isotopic signatures of Asian dust. The Hf-Nd isotope time series of eolian dust are consistent with the results of modern dust except two samples that have extremely radiogenic Hf for their Nd (epsilon-Hf =+8.6 and +10.3, epsilon-Nd =39.5 and 39.8). These data may point to a source contribution of dust unresolved by Nd and Pb isotopes. The Hf IC of eolian dust input to the oceans may be more variable and more radiogenic than previously anticipated. The Hf signature of Pacific seawater, however, has varied little over the past 20 Myr, especially across the drastic increase of eolian dust flux from Asia around 3.5 Ma. Therefore, continental contributions to seawater Hf appear to be riverine rather than eolian. Current predictions regarding the relative proportions of source components to seawater Hf must account for the presence of a variable and radiogenic continental component. Data on the IC and flux of river-dissolved Hf to the oceans are urgently required to better estimate contributions to seawater Hf. This then would permit the use of Hf isotopes as a monitor of past changes in erosion.

班公湖带多不杂超大型富金斑岩铜矿床的成岩成矿年代学、岩石学及高氧化岩浆¬流体-成矿作用

Duobuza copper deposit, newly discovered typical gold-rich porphyry copper deposit with superlarge potential, is located in the Tiegelong Mesozoic tectonic -magmatic arc of the southern edge of Qiangtang block and the northern margin of Bangonghu-Nujiang suture. Quartz diorite porphyrite and grandiorite porphyry, occurred in stock, are the main ore-bearing porphyries. As the emplacement of porphyry stock, a wide range of hydrothermal alteration has developed. Within the framework of the ore district, abundant hydrothermal magnetite developed, and the relationship between precipitation of copper and gold and hydrothermal magnetite seems much close. Correspondingly, a series of veinlets and network veinlets occurred in all alteration zones. Therefore, systematic research on such a superlarge high-grade Duobuza gold-rich porphyry copper deposit can fully revealed the metallogenic characteristics of gold-rich porphyry copper deposits in this region, establish metallogenetic model and prospecting criteria, and has important practical significance on the promotion of regional exploration. In addition, this research on it can enrich metallogenic theory of strong oxidation magma-fluid to gold-rich porphyry copper deposit, and will be helpful to understand the metallogenic characteristics in early of subduction of Gangdese arc stages and its entire evolution history of the Qinghai-Tibet Plateau, the temporal and spatial distribution of ore deposits and their geodynamics settings. Northern ore body of Duobuza copper deposit have been controlled with width (north-south) about 100 ~ 400 m, length (east-west) about 1400 m, dip of 200 °, angle of dip 65 °~ 80 °. And controlled resource amount is of 2.7 million tons Cu with grade 0.94% and 13 tons Au with 0.21g/tAu. Overall features of ore body are large scale, higher grade copper, gold-rich. Ore occurred in the body of granodiotite porphyry and quartz diorite porphyrite and its contact zone with wall rock. Through the detailed mapping and field work studies, some typies of alteration are identificated as follows: albitization, biotititation, sericitization, silication, epidotization, chloritization, carbonatization, illitization, kaolinization and so on. The range of alteration is more than 10km2. Wall alteration zone can be divided into potassic alteration, moderate argillization alteration, argillization, illite-hydromuscovite or propylitization from ore-bearing porphyry center outwards, but phyllic alteration has not well developed and only sericite-quartz veins occurred in local area. Moreover, micro-fracture is development in ore district , and correspondingly a series of veinlets are development as follows: biotite vein (EB type), K-feldspar-biotite-chalcopyrite-quartz vein, magnetite-antinolite-K-feldspar vein, quartz-chalcopyrite-magnetite veins (A-type), quartz-magnetite-biotite-K-feldspar vein, chalcopyrite veinlets in potassic alteration zone; (2) chalcopyrite occurring in the center vein–quartz vein (B type), chalcopyrite veinlets, chalcopyrite-gypsum vein in intermediate argillization alteration; (3) chalcopyrite- pyrite-quartz vein, pyrite-quartz vein, chalcopyrite-gypsum veins, quartz-gypsum- molybdenite-chalcopyrite vein in argillization alteration; (4) gypsum veins, quartz-(molybdenite)-chalcopyrite vein, quartz-pyrite vein, gypsum- chalcopyrite vein, potassium feldspar veinlets, Carbonate veins, quartz-magnetite veins in the wall rock. In short, various veins are very abundant within the framework of the ore district. The results of electronic probe microscopy analysis (EMPA) indicate that Albite (Ab 91.5~99.7%) occurred along the rim of plagioclase phenocryst and fracture, and respresents the earliest stages of alteration. K-feldspar (Or 75.1~96.9%) altered plagioclase phenocryst and matrix or formed secondary potassium feldspar veinlets. Secondary biotite occurred mainly in phenocryst, matrix and veinlets, belong to magnesium-rich biotite formed under the conditions of high-oxidation magma- hydrothermal. Chloritization developed in all alteration zones and alterd iron- magnesium minerals such as biotite and hornblende and then formed chlorite veinlets. As the temperature rises, Si in the tetrahedral site of chlorite decreased, and chlorite component evolved from diabantite to ripiolite. The consistent 280℃~360℃ of formation temperature hinted that chlorite formed on the same temperature range in all alteration zones. However, formation temperature range of chlorite from the gypsum-carbonate-chlorite vein was 190℃~220℃, and it may be the product of the latest stage of hydrothermal activity. The closely relationship between biotite and rutile indicate that most of rutiles are precipitated in the process of biotite alteration and recrystallization. In addition, the V2O3 concentration of rutile from ore body in Duobuza gold-rich porphyry copper deposit is >0.4％, indicate that V concentration in rutile has important significance on marking main ore body of porphyry copper deposit. Apatites from Duobuza deposit all are F-rich. And apatite in the wall rock contained low MnO content and relatively high FeO content, which may due to the basaltic composition of the wall rocks. The MnO in apatite from altered porphyry show a strong positive correlation with FeO. In addition, Cl/F ratio of apatite from wall rock was highest, followed by the potassic alteration zone and potassic alteration zone overprinted by moderate argillization alteration was the lowest. SO2 in Apatite are in the scope of 0 to 0.66%, biotite in the apatite has the highest SO2, followed by the potassic alteration zone, potassic alteration zone overprinted by moderate argillization alteration, and the lowest in the surrounding rocks, which may be caused by the decrease of oxygen fugacity of hydrothermal fluid and S exhaust by sulfide precipitation in potassic alteration. Magnetite in the wall rock have higher Cr2O3 and lower Al2O3 features compared with altered porphyry, this may be due to basalt wall rock generally has high Cr content. And magnetites have higher TiO2 content in potassic alteration than moderate argillization alteration overprinted by potassic alteration, argillization and wall rock, suggested that its formation temperature in potassic alteration was the highest among them. The ore minerals mainly are chalcopyrite and bornite, and Au contents of chalcopyrite, bornite, and pyrite are similar with chalcopyrite slightly higher. The Eu* negative anomaly of disseminated chalcopyrite was relatively lower than chalcopyrite in veinlets. Within a drill hole, the Eu* negative anomaly of disseminated chalcopyrite was gradually larger from bottom to top. Magnetite has the same distribution model, with obvious negative Eu* abnormal, and ΣREE in great changes. The gypsum has the highest ΣREE content and the obvious negative anomaly, and biotite obviously has the Eu* abnormal. Based on the petrographic and geochemical characteristics, five series of magmatic rocks can be broadly classified; they are volcanic rocks of the normal island arc, high-Nb basaltic rocks, adakites, altered porphyry and diorite. The Sr, Nd, Hf isotopes and geochemistry of various series of magmatic rock show that they may be the result of mixing between basic magma and various degrees of acid magma coming from lower crust melted by high temperature basic underplating from partial melting of the subduction sediment melt metasomatic mantle wedge. Furthermore S isotope and Pb isotope of the sulfide, ore-bearing porphyries and volcanic rocks indicated ore-forming source is the mantle wedge metasomatied by subduction sediment melt. Oxygen fugacity of magma estimated by Fe2O3/FeO of whole rock and zircon Ce4+/Ce3+ indicated that the oxidation of basalt-andesitic rocks is higher than ore-forming porphyry, and might imply high-oxidation characteristics of underplated basic magma. Its high oxidative mechanism is likely mantle sources metasomatied by subduction sediment magma, including water and Fe3+. And such high oxidation of basaltic magma is conducive to the mantle of sulfides in the effective access to melt. And the An component of dark part within plagioclase phenocryst zoning belong to bytownite (An 74%), and its may be a result of magma composition changes refreshment by basaltic magma injection. SHRIMP zircon U-Pb and LA-ICP-MS zircon U-Pb geochronology study showed that the intrusions and volcanic rocks from Duobuza porphyry copper deposit belong to early Cretaceous magma series (126~105Ma). The magma evolution series are as follows: the earliest diorite and diorite porphyrite → ore-bearing porphyry and barren grandiorite porphyry →basaltic andesite → diorite porphyrite → andesite → basaltic andesite, and magma component shows a evolution trend from intermediate to intermediate-acid to basic. Based on the field evidences, the formation age of high-Nb basalt may be the latest. The Ar-Ar geochronology of altered secondary biotite, K-feldspar and sericite shows that the main mineralization lasting a interval of about 4 Ma, the duration limit of whole magma-hydrothermal evolution of about 6 Ma, and possibly such a long duration limit may result in the formation of Duobuza super-large copper deposit. Moreover, tectonic diagram and trace element geochemistry of volcanic rocks and diorite from Duobuza porphyry copper deposit confirm that it formed in a continental margin arc environment. Zircon U-Pb age of volcanic rocks and porphyry fall in the range of 105~121Ma, and Duobuza porphyry copper deposit locating in the north of the Bangonghu- Nujiang suture zone, suggested that Neo-Tethys ocean still subducted northward at least early Cretaceous, and its closure time should be later than 105 Ma. Three major inclusion types and ten subtypes are distinguished from quartz phenocrysts and various quartz veins. Vapor generally coexisting with brine inclusions, suggest that fluid boiling may be the main ore-forming mechanism. Raman spectrums of fluid inclusions display that the content of vapor and liquid inclusion mainly contain water, and vapor occasionally contain a little CO2. In addition, the component of liquid inclusions mainly include Cl-, SO42-, Na+, K+, a small amount of Ca2+, F-; and Cl- and Na+ show good correlation. Vapor mainly contains water, a small amount of CO2, CH4 and C2H6 and so on. The daughter minerals identified by Laman spectroscopy and SEM include gypsum, chalcopyrite, halite, sylvite, rutile, potassium feldspar, Fe-Mn-chloride and other minerals, and ore-forming fluid belong to a complex hydrothermal system containing H2O-NaCl-KClFeCl2CaCl2. H and O isotopic analysis of quartz phenocryst, vein quartz, magnetite, chlorite and gypsum from all alteration zones show that the ore-forming fluid of Duobuza gold-rich porphyry copper deposit consisted mainly of magmatic water, without addition of meteric water. Duobuza gold-rich porphyry copper deposit formed by the primary magmatic fluid (600-950C), which has high oxidation, ultra-high salinity and metallogenic element-rich, exsolution direct from the magma, and it is representative of the typical orthomagmatic end member of the porphyry continuum. Moreover, the fluid evolution model of Duobuza gold-rich porphyry copper deposit has been established. Furthermore, two key factors for formation of large Au-rich porphyry copper deposit have been summed up, which are ore-forming fluids earlier separated from magma and high oxidation magma-mineralization fluid system.

Petrologic and geochemical characterization of São Jorge island volcanism, Azores

The island of São Jorge (38º 45’ 24’’ N - 28º 20’ 44’’W and 38º 33’ 00’’ N - 27º 44’ 32’’ W) is one of the nine islands of the Azores Archipelago that is rooted in the Azores Plateau, a wide and complex region which encompasses the triple junction between the American, Eurasia and Nubia plates. São Jorge Island has grown by fissural volcanic activity along fractures with the regional WNW-ESE trend, unveiling the importance of the regional tectonics during volcanic activity. The combination of the volcanostratigraphy (Forjaz & Fernandes, 1975; and Madeira, 1998) with geochronological data evidences that the island developed during two main volcanic phases. The first subaerial phase that occurred between 1.32 and 1.21 Ma ago (Hildenbrand et al. 2008) is recorded on the lava sequence forming the cliff at Fajã de São João, while the second phase started at 757 ka ago, is still active, and edified the rest of the island. This second phase edified the east side of the island that corresponds to Topo Volcanic Complex, in the period between 757 and 543 ka ago, while the west side named Rosais Volcanic Complex, started at 368 ka ago (Hildenbrand et al. 2008) and was still active at 117 ka ago. After the onset of Rosais, volcanic activity migrates to the center of São Jorge edifying Manadas Volcanic Complex. The volcanism on São Jorge is dominantly alkaline, with a narrow lithological composition ranging between the basanites/tefrites through the basaltic trachyandesites, in spite of this the two volcanic phases show distinct mineralogical, petrographic and geochemical characteristics that should be related with different petrogenetic conditions and growth rates of the island. Abstract viii During the first volcanic phase, growth rates are faster (≈3.4 m/ka), the lavas are slightly less alkaline and plagioclase-richer, pointing to the existence of a relative shallow and dynamic magma chamber where fractional crystallization associated with gravitational segregation and accumulation processes, produced the lavas of Fajã de São João sequence. The average growth rates during the second volcanic phase are lower (≈1.9 m/ka) and the lavas are mainly alkaline sodic, with a mineralogy composed by olivine, pyroxene, plagioclase and oxide phenocrysts, in a crystalline groundmass. The lavas are characterized by enrichment in incompatible trace element and light REE, but show differences for close-spaced lavas that unveil, in some cases, slight different degrees of fertilization of the mantle source along the island. These differences might also result from higher degrees of partial melting, as observed in the early stages of Topo and Rosais volcanic complexes, of a mantle source with residual garnet and amphibole, and/or from changing melting conditions of the mantle source as pressure. The subtle geochemical differences of the lavas contrast with the isotopic signatures, obtained from Sr-Nd-Pb-Hf isotopes, that São Jorge Island volcanism exhibit along its volcanic complexes. The lavas from Topo Volcanic Complex and from the submarine flank, i.e. the lavas located east of Ribeira Seca Fault, sample a mantle source with similar isotopic signature that, in terms of lead, overlaps Terceira Island. The lavas from Rosais and Manadas volcanic complexes, the western lavas, sample a mantle source that becomes progressively more distinct towards the west end of the island and that, in terms of lead isotopes, trends towards the isotopic composition of Faial Island. The two isotopic signatures of São Jorge, observed from the combination of lead isotopes with the other three systems, seem to result from the mixing of three distinct end-members. These end-members are (1) the common component related with the Azores Plateau and the MAR, (2) the eastern component with a FOZO signature and possibly related with the Azores plume located beneath Terceira, and (3) the western component, similar to Faial, where the lithosphere could have been entrained by an ancient magmatic liquid, isolated for a period longer than 2Ga. The two trends observed in the island reinforce the idea of small-scale mantle heterogeneities beneath the Azores region, as it has been proposed to explain the isotopic diversity observed in the Archipelago.

Dating coeval mafic magmatism and ultrahigh temperature metamorphism in the Anapolis-Itaucu Complex, Central Brazil

Dating granulites has always been of great interest because they represent one of the most extreme settings of an orogen. Owing to the resilience of zircon, even in such severe environments, the link between P-T conditions and geological time is possible. However, a challenge to geochronologists is to define whether the growth of new zircon is related to pre- or post-P-T peak conditions and which processes might affect the (re) crystallization. In this context, the Anapolis-Itaucu Complex, a high-grade complex in central Brazil with ultrahigh temperature (UHT) granulites, may provide valuable information within this topic. The Anapolis-Itaucu Complex (AIC) includes ortho- and paragranulites, locally presenting UHT mineral assemblages, with igneous zircon ages varying between 760 and 650 Ma and metamorphic overgrowths dated at around 650-640 Ma. Also common in the Anapolis-Itaucu Complex are layered mafic-ultramafic complexes metamorphosed under high-grade conditions. This article presents the first geological and geochronological constraints of three of these layered complexes within the AIC, the Damolandia, Taquaral and Goianira-Trindade complexes. U-Pb (LA-MC-ICPMS, SHRIMP and ID-TIMS) zircon analyses reveal a spread of concordant ages spanning within an age interval of similar to 80 Ma with an ""upper"" intercept age of similar to 670 Ma. Under cathodoluminescence imaging, these crystals show partially preserved primary sector zoning, as well as internal textures typical of alteration during high-grade metamorphism, such as inward-moving boundaries. Zircon grains reveal homogeneous initial (176)Hf/(177)Hf values in distinct crystal-scale domains in all samples. Moreover. Hf isotopic ratios show correlation neither with U-Pb ages nor with Th/U ratios, suggesting that zircon grains crystallized during a single growth event. It is suggested, therefore, that the observed spread of concordant U-Pb ages may be related to a memory effect due to coupled dissolution-reprecipitation process during high grade metamorphism. Therefore, understanding the emplacement and metamorphism of this voluminous mafic magmatism is crucial as it may represent an additional heat source for the development of the ultrahigh temperature paragenesis recorded in the paragranulites. (C) 2010 Elsevier B.V. All rights reserved.

Geochemistry of Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

A geochemical study of crustal plutonic rocks from the southern Mariana Trench forearc: Relationship to volcanic rocks erupted during subduction initiation

Two suites of intermediate-felsic plutonic rocks were recovered by dredges RD63 and RD64 (R/V KK81-06-26) from the northern wall of the Mariana trench near Guam, which is located in the southern part of the Izu-Bonin-Mariana (IBM) island arc system. The locations of the dredges are significant as the area contains volcanic rocks (forearc basalts and boninites) that have been pivotal in explaining processes that occur when one lithospheric plate initially begins to subduct beneath another. The plutonic rocks have been classified based on petrologic and geochemical analyses, which provides insight to their origin and evolution in context of the surrounding Mariana trench. Based on whole rock geochemistry, these rocks (SiO2: 49-78 wt%) have island arc trace element signatures (Ba, Sr, Rb enrichment, Nb-Ta negative anomalies, U/Th enrichment), consistent with the adjacent IBM volcanics. Depletion of rare earth elements (REEs) relative to primitive mantle and excess Zr and Hf compared to the middle REEs indicate that the source of the plutonic rocks is similar to boninites and transitional boninites. Early IBM volcanic rocks define isotopic fields (Sr, Pb, Nd and Hf-isotopes) that represent different aspects of the subduction process (e.g., sediment influence, mantle provenance). The southern Mariana plutonic rocks overlap these fields, but show a clear distinction between RD63 and RD64. Modeling of the REEs, Zr and Hf shows that the plutonic suites formed via melting of boninite crust or by crystallization from a boninite-like magma rather than other sources that are found in the IBM system. The data presented support the hypothesis that the plutonic rocks from RD63 and RD64 are products of subduction initiation and are likely pieces of middle crust in the forearc exposed at the surface by faulting and serpentine mudvolcanoes. Their existence shows that intermediate-felsic crust may form very early in the history of an intra-oceanic island arc system. Plutonic rocks with similar formation histories may exist in obducted suprasubduction zone ophiolites and would be evidence that felsic-intermediate forearc plutonics are eventually accreted to the continents.