Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Low delta18O zircon grains in the Neoarchean Rum Jungle Complex, northern Australia: An indicator of emergent continental crust

The timing of widespread continental emergence is generally considered to have had a dramatic effect on the hydrological cycle, atmospheric conditions, and climate. New secondary ion mass spectrometry (SIMS) oxygen and laser-ablation–multicollector–inductively coupled plasma–mass spectrometry (LA-MC-ICP-MS) Lu-Hf isotopic results from dated zircon grains in the granitic Neoarchean Rum Jungle Complex provide a minimum time constraint on the emergence of continental crust above sea level for the North Australian craton. A 2535 ± 7 Ma monzogranite is characterized by magmatic zircon with slightly elevated δ18O (6.0‰–7.5‰ relative to Vienna standard mean ocean water [VSMOW]), consistent with some contribution to the magma from reworked supracrustal material. A supracrustal contribution to magma genesis is supported by the presence of metasedimentary rock enclaves, a large population of inherited zircon grains, and subchondritic zircon Hf (εHf = −6.6 to −4.1). A separate, distinct crustal source to the same magma is indicated by inherited zircon grains that are dominated by low δ18O values (2.5‰–4.8‰, n = 9 of 15) across a range of ages (3536–2598 Ma; εHf = −18.2 to +0.4). The low δ18O grains may be the product of one of two processes: (1) grain-scale diffusion of oxygen in zircon by exchange with a low δ18O magma or (2) several episodes of magmatic reworking of a Mesoarchean or older low δ18O source. Both scenarios require shallow crustal magmatism in emergent crust, to allow interaction with rocks altered by hydrothermal meteoric water in order to generate the low δ18O zircon. In the first scenario, assimilation of these altered rocks during Neoarchean magmatism generated low δ18O magma with which residual detrital zircons were able to exchange oxygen, while preserving their U-Pb systematics. In the second scenario, wholesale melting of the altered rocks occurred in several distinct events through the Mesoarchean, generating low δ18O magma from which zircon crystallized. Ultimately, in either scenario, the low δ18O zircons were entrained as inherited grains in a Neoarchean granite. The data suggest operation of a modern hydrological cycle by the Neoarchean and add to evidence for the increased emergence of continents by this time

碎屑锆石年龄和Nd-Hf同位素组成对扬子基底演化的制约

The South China craton was formed by the collision of the Yangtze and Cathaysia blocks during the Neoproterozoic Jiangnan orogeny (also termed as the Jingnin or Sibao orogeny in Chinese literature). Basement rocks within the Yangtze block consist mainly of Proterozoic sediments of the Lengjiaxi and Banxi Groups. U-Pb ages of detrital zircons obtained by the LA-ICP-MS dating technique imply that the deposition of the Lengjiaxi Group continued until the Neoproterozoic. The youngest detrital zircons suggest a maximum deposition age of ~830 Ma for the Lengjiaxi Group, consistent with the initiation time of the deposition of the overlying Banxi Group, likely indicating continuous deposition of these two groups and a short temporal hiatus (~10 Ma) between the Neoproterozoic sedimentary rocks distributed in the South China craton. Detrital zircons from both the Lengjiaxi and Banxi Groups have a wide range of εHf(t) values from -12 to 14.2 and a continuous Nd and Hf model age spectrum from ~820 Ma to 2200 Ma. Some grains have model ages ranging up to ca. 2.9-3.5 Ga, indicating that both juvenile mantle material and ancient crust provided sedimentary detritus. This is also consistent with the Nd isotopic signature of sedimentary rocks recorded in the Lengjiaxi Group, suggesting a back-arc tectonic setting. The Banxi Group has slightly enriched Nd isotopic signatures relative to the Lengjiaxi Group, implying a higher percentage of old continental material in the sedimentary source. Combined with previously published data, new results can help us to reconstruct the Neoproterozoic tectonic evolution of the South China craton. The age spectrum of detrital zircons and Nd-Hf isotopic composition suggests a two-stage collision: Between 1000 Ma to 870 Ma, a continental magmatic arc was build up along the eastern margin of the Yangtze block. Convergence led to continent-based back-arc extension, subsidence and formation of a back-arc basin. Detritus originating from arc-related magmatic and old basement rocks was transported into this back-arc basin resulting in formation of the Lengjiaxi Group and its equivalents. At around 870 Ma, a second (oceanic) arc was formed by extension of an inter-arc basin, subduction subsequently led to the first collision and the emplacement of the blueschist mélange. Accretion of the magmatic arc lasted until the closure of an oceanic basin between the Yangtze and Cathaysia blocks at about 830 Ma. Shortly after the collision, subsequent uplift, further extension of the former back-arc basin and post-collisional granitoid magmatism caused a tilting of the Lengjiaxi sediments. Between 830 Ma and 820 Ma, subsequent closure of the oceanic back-arc basin and formation of the Jiangnan orogen took place, leaving a regional unconformity above the Lengjiaxi Group. Above this unconformity the Banxi Group was immediately deposited during the post-tectonic stage.

Crystallization conditions and controls on trace element residence in the main minerals from the Pedra Branca Syenite, Brazil: An electron microprobe and LA-ICPMS study

Major and trace-element microanalyses of the main minerals from the 610 Ma Pedra Branca Syenite, southeast Brazil, allow inferences on intensive parameters of magmatic crystallization and on the partition of trace-elements among these minerals, with important implications for the petrogenetic evolution of the pluton. Two main syenite types make up the pluton, a quartz-free syenite with tabular alkali feldspar (laminated silica-saturated syenite, LSS, with Na-rich augite + phlogopite + hematite + magnetite + titanite + apatite) and a quartz-bearing syenite (laminated silica-oversaturated syenite, LSO, with scarce corroded plagioclase plus diopside + biotite +/- hornblende + ilmenite magnetite +/- titanite + apatite). Both types share a remarkable enrichment in incompatible elements as K, Ba, Sr, P and LREE. Apatite saturation temperatures of similar to 1060-1090 degrees C are the best estimates of liquidus, whereas the pressure of emplacement, based on Al-in-hornblende barometry, is estimated as 3.3 to 4.8 khan Although both units crystallized under oxidizing conditions, oxygen fugacity was probably higher in LSS, as shown by higher mg# of the mafic minerals and higher hematite contents in Hem-Ilm(ss). In contrast with the Ca-bearing alkali-feldspar from LSO, which hosts most of the whole-rock Sr and Pb, virtually Ca-free alkali-feldspar from LSS hosts similar to 50% of whole-rock Sr and similar to 80% of Pb, the remainder of these elements being shared by apatite, pyroxene and titanite. This contrast reflects a strong crystal-chemical control, whereby a higher proportion of an element with similar ratio and charge (Ca2+) enhances the residence of Sr and Pb in the M-site of alkali feldspar. The more alkaline character of the LSS magma is inferred to have inhibited zircon saturation; Zr + Hf remained in solution until late in the crystallization, and were mostly accommodated in the structure of Ca-Na pyroxene and titanite, which are one order of magnitude richer in these elements compared to the same minerals in LSO, where most of Zr and Hf are inferred to reside in zircon. The REE, Th and U reside mostly in titanite and apatite; D(REE)Tit/Ap raises steadily from 1 to 6 from La to Tb then remains constant up to Lu in the LSO sample; these values are about half as much in the LSS sample, where lower contents of incompatible elements in titanite are attributed to its greater modal abundance and earlier crystallization. (C) 2012 Elsevier B.V. All rights reserved.

Peak Last Glacial weathering intensity on the North American continent recorded by the authigenic Hf isotope composition of North Atlantic deep-sea sediments

We have retrieved radiogenic hafnium (Hf) isotope compositions (ɛHf) from authigenic Fe–Mn oxyhydroxides of deep northwest Atlantic sediments deposited over the past 26 ka to investigate the oceanic evidence of changes in dissolved weathering inputs from NE America during the last deglaciation. The extraction of seawater-derived Hf isotopic compositions from Fe–Mn oxyhydroxides is not a standard procedure. Comparisons between the Al/Hf ratios and Hf isotopic compositions of the chemically extracted authigenic phase on the one hand, and those of the corresponding detrital fractions on the other, provide evidence that the composition of past seawater has been reliably obtained for most sampled depths with our leaching procedures. This is endorsed most strongly by data for a sediment core from 4250 m water depth at the deeper Blake Ridge, for which consistent replicates were produced throughout. The Hf isotopic composition of the most recent sample in this core also closely matches that of nearby present day central North Atlantic seawater. Comparison with previously published seawater Nd and Pb isotope compositions obtained on the same cores shows that both Hf and Pb were released incongruently during incipient chemical weathering, but responded differently to the deglacial retreat of the Laurentide Ice Sheet. Hafnium was released more congruently during peak glacial conditions of the Last Glacial Maximum (LGM) and changed to typical incongruent interglacial ɛHf signatures either during or shortly after the LGM. This indicates that some zircon-derived Hf was released to seawater during the LGM. Conversely, there is no clear evidence for an increase in the influence of weathering of Lu-rich mineral phases during deglaciation, possibly since relatively unradiogenic Hf contributions from feldspar weathering were superimposed. While the authigenic Pb isotope signal in the same marine sediment samples traced peak chemical weathering rates on continental North America during the transition to the Holocene a similar incongruent excursion is notably absent in the Hf isotope record. The early change towards more radiogenic ɛHf in relation to the LGM may provide direct evidence for the transition from a cold-based to a warm-based Laurentide Ice Sheet on the Atlantic sector of North America.

Geochemistry and age determination of zircons in Cretaceous to Quaternary sediments

In central Antarctica, drainage today and earlier back to the Paleozoic radiates from the Gamburtsev Subglacial Mountains (GSM). Proximal to the GSM past the Permian-Triassic fluvial sandstones in the Prince Charles Mountains (PCM) are Cretaceous, Eocene, and Pleistocene sediment in Prydz Bay (ODP741, 1166, and 1167) and pre-Holocene sediment in AM04 beneath the Amery Ice Shelf. We analysed detrital zircons for U-Pb ages, Hf-isotope compositions, and trace elements to determine the age, rock type, source of the host magma, and "crustal" model age (T(C)DM). These samples, together with others downslope from the GSM and the Vostok Subglacial Highlands (VSH), define major clusters of detrital zircons interpreted as coming from (1) 700 to 460 Ma mafic granitoids and alkaline rock, epsilon-Hf 9 to -28, signifying derivation 2.5 to 1.3 Ga from fertile and recycled crust, and (2) 1200-900 Ma mafic granitoids and alkaline rock, epsilon-Hf 11 to -28, signifying derivation 1.8 to 1.3 Ga from fertile and recycled crust. Minor clusters extend to 3350 Ma. Similar detrital zircons in Permian-Triassic, Ordovician, Cambrian, and Neoproterozoic sandstones located along the PaleoPacific margin of East Antarctica and southeast Australia further downslope from central Antarctica reflect the upslope GSM-VSH nucleus of the central Antarctic provenance as a complex of 1200-900 Ma (Grenville) mafic granitoids and alkaline rocks and older rocks embedded in 700-460 Ma (Pan-Gondwanaland) fold belts. The wider central Antarctic provenance (CAP) is tentatively divided into a central sector with negative ?Hf in its 1200-900 Ma rocks bounded on either side by positive epsilon-Hf. The high ground of the GSM-VSH in the Permian and later to the present day is attributed to crustal shortening by far-field stress during the 320 Ma mid-Carboniferous collision of Gondwanaland and Laurussia. Earlier uplifts in the ~500 Ma Cambrian possibly followed the 700-500 Ma assembly of Gondwanaland, and in the Neoproterozoic the 1000-900 Ma collisional events in the Eastern Ghats-Rayner Province at the end of the 1300-1000 Ma assembly of Rodinia.

Trace element geochemistry of zircons frim in situ ocean lithoshere

We characterize the textural and geochemical features of ocean crustal zircon recovered from plagiogranite, evolved gabbro, and metamorphosed ultramafic host-rocks collected along present-day slow and ultraslow spreading mid-ocean ridges (MORs). The geochemistry of 267 zircon grains was measured by sensitive high-resolution ion microprobe-reverse geometry at the USGS-Stanford Ion Microprobe facility. Three types of zircon are recognized based on texture and geochemistry. Most ocean crustal zircons resemble young magmatic zircon from other crustal settings, occurring as pristine, colorless euhedral (Type 1) or subhedral to anhedral (Type 2) grains. In these grains, Hf and most trace elements vary systematically with Ti, typically becoming enriched with falling Ti-in-zircon temperature. Ti-in-zircon temperatures range from 1,040 to 660°C (corrected for a TiO2 ~ 0.7, a SiO2 ~ 1.0, pressure ~ 2 kbar); intra-sample variation is typically ~60-15°C. Decreasing Ti correlates with enrichment in Hf to ~2 wt%, while additional Hf-enrichment occurs at relatively constant temperature. Trends between Ti and U, Y, REE, and Eu/Eu* exhibit a similar inflection, which may denote the onset of eutectic crystallization; the inflection is well-defined by zircons from plagiogranite and implies solidus temperatures of ~680-740°C. A third type of zircon is defined as being porous and colored with chaotic CL zoning, and occurs in ~25% of rock samples studied. These features, along with high measured La, Cl, S, Ca, and Fe, and low (Sm/La)N ratios are suggestive of interaction with aqueous fluids. Non-porous, luminescent CL overgrowth rims on porous grains record uniform temperatures averaging 615 ± 26°C (2SD, n = 7), implying zircon formation below the wet-granite solidus and under water-saturated conditions. Zircon geochemistry reflects, in part, source region; elevated HREE coupled with low U concentrations allow effective discrimination of ~80% of zircon formed at modern MORs from zircon in continental crust. The geochemistry and textural observations reported here serve as an important database for comparison with detrital, xenocrystic, and metamorphosed mafic rock-hosted zircon populations to evaluate provenance.

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.

Large igneous provinces and silicic large igneous provinces : progress in our understanding over the last 25 years

Large Igneous Provinces are exceptional intraplate igneous events throughout Earth’s history. Their significance and potential global impact is related to the total volume of magma intruded and released during these geologically brief events (peak eruptions are often within 1-5 Myrs duration) where millions to tens of millions of cubic kilometers of magma are produced. In some cases, at least 1% of the Earth’s surface has been directly covered in volcanic rock, being equivalent to the size of small continents with comparable crustal thicknesses. Large Igneous Provinces are thus important, albeit episodic episodes of new crust addition. However, most magmatism is basaltic so that contributions to crustal growth will not always be picked up in zircon geochronology studies that better trace major episodes of extension-related silicic magmatism and the silicic Large Igneous Provinces. Much headway has been made on our understanding of these anomalous igneous events over the last 25 years, driving many new ideas and models. This includes their: 1) global spatial and temporal distribution, with a long-term average of one event approximately every 20 Myrs, but a clear clustering of events at times of supercontinent break-up – Large Igneous Provinces are thus an integral part of the Wilson cycle and are becoming an increasingly important tool in reconnecting dispersed continental fragments; 2) compositional diversity that in part reflects their crustal setting of ocean basins, and continental interiors and margins where in the latter setting, LIP magmatism can be silicicdominant; 3) mineral and energy resources with major PGE and precious metal resources being hosted in these provinces, as well as magmatism impacting on the hydrocarbon potential of volcanic basins and rifted margins through enhancing source rock maturation, providing fluid migration pathways, and trap formation; 4) biospheric, hydrospheric and atmospheric impacts, with Large Igneous Provinces now widely regarded as a key trigger mechanism for mass extinctions, although the exact kill mechanism(s) are still being resolved; 5) role in mantle geodynamics and thermal evolution of the Earth, by potentially recording the transport of material from the lower mantle or core-mantle boundary to the Earth's surface and being a fundamental component in whole mantle convection models; and 6) recognition on the inner planets where the lack of plate tectonics and erosional processes and planetary antiquity means that the very earliest record of LIP events during planetary evolution may be better preserved than on Earth.

Zircon Sand--a Viable Alternative Moulding System for Titanium Castings

The experimental observations of casting titanium in sodium silicate bonded zircon sand mould are presented in this paper. Metal-mould reactions, in general, involved dissolution of oxides in liquid titanium resulting in contamination of the casting. Minimal metal-mould reactions occurred when titanium was cast in zircon sand mould containing about 7.5 wt% of ZrO2. It has been further shown that the metal-mould reaction is considerably reduced if moulds were fired at high temperatures (> 1273K). This ensured elimination of moisture from the mould and also resulted in some beneficial changes in the mould chemistry. The reduction in metal-mould reaction is reflected in the decrease in oxygen and hydrogen contamination and decrease in hardness. Thus microhardness profile and oxygen analysis seems to provide a good index for evaluation of severity of metal-mould reaction. The method has been demonstrated to be satisfactory for casting titanium components.

RES-TOCSY: A facile approach for accurate determination of magnitudes, and relative signs of (n)J(HF)

The RES-TOCSY experiment for accurate determination of heteronuclear (n)J(HF) is reported. The main feature of the proposed technique is the accurate measurement of magnitudes of heteronuclear couplings from the displacement of cross sections of the 2D spectrum and their relative signs from the slopes of their displacement vectors. The experiment is highly advantageous as the couplings of smaller magnitudes hidden within line widths could also be accurately determined, and also in situations when the spectrum does not display any coupling fine structures. The efficient utility of the developed pulse sequence is unambiguously established on fluorine containing aromatic and aliphatic molecules. (C) 2014 Elsevier B.V. All rights reserved.