Hf Budget Research Articles

Post-UHP tectonic evolution of the East Kunlun orogenic belt, northern tibetan plateau: insight from the regional-scale crustal anatexis

ABSTRACT Extensive crustal anatexis is common during the decompressional exhumation of deeply subducted continental crust and the delamination of a collision‐thickened orogenic lithosphere, indicating that determining the timing of partial melting can provide insights into the possible tectonic evolution during orogenic processes. An integrated study of petrology, zirconology and whole-rock geochemical compositions from migmatites and pegmatites in the Nageng, Langmuri and Wulonggou area of the East Kunlun orogenic belt, is presented in this study. The protoliths of these migmatites include Tonian sedimentary rocks and ca. 440 Ma arc-related dioritic rock. Together with previous studies, an extensive crustal anatexis event recorded by anatectic zircons occurred after ca. 410 Ma. In addition, hafnium isotope analyses indicate that the anatectic zircons may or may not inherit their Hf isotope compositions from protolith zircons during partial melting, depending on whether or not the garnet Hf contributes to the Hf budget of anatectic melt. Thus, the most reasonable method to trace the source of granite is to compare the Hf isotope composition of anatectic zircon in migmatite and magmatic zircon in contemporaneous granite. By such method, anatectic melt produced by migmatites in this study could account for both penecontemporaneous A- and I-type granites with high magmatic zircon εHf(t) values and S-type granites with low magmatic zircon εHf(t) values. As the extensive crustal anatexis is later than both metamorphic peak and amphibole-facies retrogression of high-pressure and ultrahigh-pressure (HP-UHP) metamorphic rocks, it is reasonable that post-collision orogenic collapse of the collision‐thickened orogenic lithosphere as a result of delamination and asthenospheric upwelling occurred after ca. 410 Ma, which is also supported by contemporaneous granulite-facies metamorphism, molasse deposition, and magmatic events including Xiarihamu mafic-ultramafic intrusions, A-type granites, and mafic dykes formed in the continental rifting setting.

Hafnium Isotopic Composition of the Bushveld Complex Requires Mantle Melt–Upper Crust Mixing: New Evidence from Zirconology of Mafic, Felsic and Metasedimentary Rocks

Abstract The origin of magmas that formed the Bushveld Complex remains highly debated in spite of many decades of intense research. Previous geochemical–petrological studies have shown a strong mantle derivation resulting ultimately in highly economic ore bodies of platinum group elements and chromium. However, geochemistry also points to the contribution of a significant crustal component, which may have been derived singly or in combination from a number of different sources. These include subcontinental lithospheric mantle that was enriched prior to Bushveld magma formation, possibly by subduction, assimilation of lower and upper crust during magma ascent, and contamination during magma chamber accretion within sedimentary rocks of the enclosing Transvaal Supergroup. In this study, the contributions of these various reservoirs will be evaluated by employing Hf isotopic data of well-characterized zircon grains in mafic, felsic and metasedimentary rocks, together with Zr–Hf bulk-rock compositions. The results reveal that magmatic zircon grains in mafic cumulate rocks from the floor to the roof of the c. 9 km thick Rustenburg Layered Suite (RLS) show essentially the same variations in εHf2·055 Ga from −7·5 to −10·2 as those of metamorphic zircon grains and overgrowths in the immediate surrounding quartzite and metapelitic rocks, as well as in granitic melt batches, granophyres, and the upper Rooiberg volcanics. The same values are also obtained by estimating the average Hf isotopic compositions of detrital zircon grains in many quartzite and metapelitic rocks from the surrounding Magaliesberg (εHf2·055 Ga = −6·2 to −10·8, six samples, maximum deposition age at 2080 Ma) and Houtenbeck formations (εHf2·055 Ga = −7·1 to −8·9, three samples, maximum deposition age at 2070 Ma), and by a six-point isochron of a garnet-schist from the Silverton Formation (εHft = −6·6 ± 0·7; age = 2059·4 ± 2·7 Ma). Zircon morphologies, zoning patterns, Hf isotopic data and petrological constraints furthermore reveal that metamorphic zircon was precipitated from aqueous fluids and/or felsic melts at temperatures between 550 and 900 °C, and that the Hf isotopic composition became homogenized during fluid transport in the contact aureole. However, results of numerical modelling indicate that fluid infiltration had only a minor effect on the Zr–Hf budget and Hf isotopic composition of the RLS, and that these parameters were mainly controlled by the mixing of melts derived from three major sources: (1) the asthenospheric mantle (>20 %); (2) enriched subcontinental lithospheric mantle (<80 %); (3) assimilation of significant amounts of crust (up to 40 %). The modelling furthermore suggests that assimilation of lower Kaapvaal Craton crust was minor (<15 %) during B1 (high-Mg andesite) magma formation, but up to 40 % during B3 (tholeiite) magma formation. The minor variation in εHft of zircon throughout the entire stratigraphy of the RLS resulted from the interplay of three dominant contributing factors: (1) intrusion of hot (>1200 °C) mantle-derived magmas with relatively low Zr–Hf concentrations having a similar εHf2·055 Ga of −8·5 ± 1·9 to that of upper crust rocks surrounding the RLS; (2) significant assimilation of volcanic and metasedimentary rocks with high Zr–Hf concentration; (3) mingling, mixing and/or diffusive exchange of Zr and Hf between crust and mantle-derived melts and aqueous fluids prior to late-magmatic crystallization of zircon at temperatures between 700 and 900 °C. This study shows that the combination of Zr–Hf bulk-rock data with Hf isotopic data of well-characterized zircon grains provides a powerful tool to quantify various mantle and crustal reservoirs of mafic layered intrusions, and allows new insights into magma chamber and related contact metamorphic processes.

BEOL Post-Etch Clean Robustness Improvement with Ultra-Diluted Hf for 28nm Node

For 28 nm and beyond, severe specifications in terms of dimensions and materials integrity still drive further cleaning process improvements. As the global “HF budget” drastically decreases with interconnections dimensions, HF solution dilution and process time both decreased stepwise. However, very short recipes with process time shorter than 15s start to suffer from lack of robustness, in particular for the monitoring of inline parameters such as flow-rates and temperature. In this paper, we highlighted that a first matching of silicon oxide consumption was usefull to select temperature and concentration range for the diluted HF solution. High dilution ratio, and “room temperature” (20 °C) were then selected. Variations in cleaning efficiency were analyzed as regard with electrical defects density at three metals levels, then the use of 0.025 %wt. HF, 20 °C, 40 s. was pointed out as the more promising solution for process of record replacement. Process robustness, i.e. inline monitoring data collection and uniformity on wafer should thus be improved thanks to this longer process time and a lower process temperature.

Trace element partitioning and Lu–Hf isotope systematics in spinel peridotites from the Rio Grande Rift and Colorado Plateau: Towards improved age assessment of clinopyroxene Lu/Hf–176Hf/177Hf in SCLM peridotite

Our study of Colorado Plateau and Rio Grande rift spinel peridotite xenoliths determined bulk Lu–Hf budgets and cpx, opx, and whole rock 176Hf/177Hf to evaluate the potential age significance of Lu/Hf–Hf isotope correlations in sub-continental lithospheric mantle (SCLM) derived xenoliths. The samples have fertilities (spinel Cr# range from 0.1 to 0.5), and equilibration temperatures (950–1050°C) that overlap with those of spinel peridotites commonly used in Lu–Hf dating studies. The Lu/Hf of clinopyroxene (cpx) and its associated whole rock (WR) are similar in fertile samples, but cpx has a lower Lu/Hf than that of the WR in refractory samples. Orthopyroxene (opx) has systematically higher Lu/Hf than cpx, but in many samples, the opx and cpx have identical 176Hf/177Hf, suggesting that the Hf isotope composition of these minerals is supported by the Lu/Hf of the WR rather than that of the individual minerals. Many opx fractions and whole rocks have less radiogenic 176Hf/177Hf than their corresponding cpx (but similar to that of the host magma), reflecting contamination. Because the 176Hf/177Hf of cpx is supported by the WR Lu/Hf, it is necessary to use the latter rather than the cpx Lu/Hf for isochron dating. However, because the actual WR Lu/Hf values are susceptible to secondary overprinting, we recommend using model WR Lu/Hf values (determined from mineral Lu and Hf concentrations and modal abundances) to construct external cpx isochrons. Model WR and measured cpx 176Hf/177Hf are correlated (r2=0.98) in a suite of eastern Colorado Plateau xenoliths and yield an apparent age of 1.2Ga (versus 1.5Ga when – incorrectly – using cpx Lu/Hf). Despite the good correlation between Lu/Hf and 176Hf/177Hf, we do not find correlations between indicators of melt depletion and Lu/Hf or 176Hf/177Hf. This suggests that Lu/Hf–176Hf/177Hf correlations are not the result of melt depletion. Instead, we propose that Lu/Hf–176Hf/177Hf correlations are the result of mixing between depleted and enriched components (e.g. metasomatism of depleted lithospheric mantle). We emphasize that additional data should be utilized (e.g. whole rock Lu–Hf budget, degree of metasomatism, opx 176Hf/177Hf) when interpreting apparent Lu–Hf isochrons for age significance.

Controls on the incongruent release of hafnium during weathering of metamorphic and sedimentary catchments

It is well established that Hf weathers incongruently such that the isotopic compositions in seawater are offset from those of Nd relative to the correlation defined by bulk lithologies of the continental crust. Here we study this process in detail with new records of the seasonal variability of isotope compositions and concentrations of Hf and Nd in four Swiss rivers. The water has been filtered at a pore size of 0.45μm and therefore represents the truly dissolved and the colloidal pool of both elements. The studied rivers drain metamorphic (gneissic) or sedimentary (mixed carbonate/siliciclastic) lithologies. The dissolved isotope data are compared to the isotope compositions and concentrations of the suspended load and different fractions of the actual source rocks in the respective catchments, as well as to concomitant changes in the aqueous chemistry of the major elements.Dissolved Nd concentrations span similar ranges for all rivers, whereas Hf concentrations are one order of magnitude lower in the rivers that drain gneissic catchments compared to those draining sedimentary rocks. This primarily results from the retention of most of the Hf in the gneissic zircons, as indicated by the Hf budget of the gneisses, whereas Hf in the sedimentary catchments is readily weathered from fine detrital silicates.Large differences are found between the dissolved Hf isotope compositions of the rivers and those of the suspended load and the source rocks, consistent with the release of Hf from a radiogenic rock fraction during weathering. In the metamorphic catchments this primarily reflects that fact that zircons are barely accessible for weathering. The zircon-free portion of the rocks appears to weather congruently as the riverine Hf isotope compositions are similar to the zircon-free portion of the gneisses, rather than being distinctly more radiogenic. Leaching experiments performed to understand the riverine Hf budget in the sedimentary catchments reveal that the carbonate fraction of the sedimentary rocks is extremely radiogenic, yielding Hf isotope compositions up to εHf of +208. However, the Hf concentrations in the carbonate fractions are too low to dominate the riverine Hf budget, which is instead controlled by the weathering of detrital silicate minerals.Two of the catchments, a metamorphic and a sedimentary one, show relatively systematic changes towards more radiogenic dissolved Hf isotope compositions as discharge increases. This suggests that continental runoff conditions could be a relevant parameter for the control of the seawater Hf isotope composition, whereby more congruent weathering is achieved during low discharge when Hf is increasingly derived from weathering-resistant unradiogenic minerals.

Hf and Nd isotopes in marine sediments: Constraints on global silicate weathering

The combined use of Lu–Hf and Sm–Nd isotope systems potentially offers a unique perspective for investigating continental erosion, but little is known about whether, and to what extent, the Hf–Nd isotope composition of sediments is related to silicate weathering intensity. In this study, Hf and Nd elemental and isotope data are reported for marine muds, leached Fe-oxide fractions and zircon-rich turbidite sands collected off the Congo River mouth, and from other parts of the SE Atlantic Ocean. All studied samples from the Congo fan (muds, Fe-hydroxides, sands) exhibit indistinguishable Nd isotopic composition (ε Nd ~ − 16), indicating that Fe-hydroxides leached from these sediments correspond to continental oxides precipitated within the Congo basin. In marked contrast, Hf isotope compositions for the same samples exhibit significant variations. Leached Fe-hydroxide fractions are characterized by ε Hf values (from − 1.1 to + 1.3) far more radiogenic than associated sediments (from − 7.1 to − 12.0) and turbidite sands (from − 27.2 to − 31.6). ε Hf values for Congo fan sediments correlate very well with Al/K (i.e. a well-known index for the intensity of chemical weathering in Central Africa). Taken together, these results indicate that (1) silicate weathering on continents leads to erosion products having very distinctive Hf isotope signatures, and (2) a direct relationship exists between ε Hf of secondary clay minerals and chemical weathering intensity. These results combined with data from the literature have global implications for understanding the Hf–Nd isotope variability in marine precipitates and sediments. Leached Fe-hydroxides from Congo fan sediments plot remarkably well on an extension of the ‘seawater array’ (i.e. the correlation defined by deep-sea Fe–Mn precipitates), providing additional support to the suggestion that the ocean Hf budget is dominated by continental inputs. Fine-grained sediments define a diffuse trend, between that for igneous rocks and the ‘seawater array’, which we refer to as the ‘zircon-free sediment array’ (ε Hf = 0.91 ε Nd + 3.10). Finally, we show that the Hf–Nd arrays for seawater, unweathered igneous rocks, zircon-free and zircon-bearing sediments (ε Hf = 1.80 ε Nd + 2.35) can all be reconciled, using Monte Carlo simulations, with a simple weathering model of the continental crust.

The control of weathering processes on riverine and seawater hafnium isotope ratios

Hafnium 176 Hf/ 177 Hf isotope ratio variations in marine records are thought to reflect changes in continental weathering through time, but the behavior of Hf in rivers, and during weathering, is not well understood. Here, we present 176 Hf/ 177 Hf data for rivers, bedrock, soils, and leaching experiments for the Moselle basin, Vosges, France. These data strongly suggest that the 176 Hf/ 177 Hf composition of river waters is controlled by prefer- ential dissolution of accessory phases (i.e., apatite, sphene) versus more resistant minerals (e.g., K-feldspar) and linked to the intensity of silicate weathering. Estimates for the global isotopic composition of riverine Hf suggest that the ocean Hf budget may be dominated by river input, and variations seen in marine records can be directly related to changes in silicate weathering intensity.

Hf isotopes of MARID (mica-amphibole-rutile-ilmenite-diopside) rutile trace metasomatic processes in the lithospheric mantle

The Hf isotope composition of rutile in mica-amphibole-rutile-ilmenite-diopside (MARID) xenoliths from the Kimberley area of South Africa has been analyzed in situ by laser ablation microprobe–multicollector–inductively coupled plasma mass spectrometry to investigate metasomatic processes in the lithospheric mantle. The 176Hf/177Hf ratio shows a wide range, from 0.2811 to 0.2858 (eHf = −55 to +110); much of this range is found within single samples and even within single grains. We suggest that the MARID rutiles initially resulted from the interaction of an asthenospheric melt with ancient depleted harzburgitic mantle with low 176Hf/177Hf ratios (<0.2812) and Lu/Hf ratios of ∼0.04, that dominated their Hf budget. The MARID rocks were later metasomatized by a fluid and/or melt that had caused the breakdown of eclogitic or lherzolitic garnet with Lu/Hf ratios of ∼0.6, providing a source of highly radiogenic Hf. The low 176Hf/177Hf ratios preserved in some MARID rutiles show that the Nd-Hf isotope systematics of kimberlites and lamproites can be explained by mixing between an asthenospheric melt and the ancient subcontinental lithospheric mantle.

New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts

The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters. For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific ε Nd and ε Hf both decrease with water depth. Similarly, ε Nd and ε Hf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable. The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific. Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation.

Tracing the history of submarine hydrothermal inputs and the significance of hydrothermal hafnium for the seawater budget—a combined Pb–Hf–Nd isotope approach

Secular variations in the Pb isotopic composition of a mixed hydrogenous-hydrothermal ferromanganese crust from the Bauer Basin in the eastern Equatorial Pacific provide clear evidence for changes in hydrothermal contributions during the past 7 Myr. The nearby Galapagos Rise spreading center provided a strong hydrothermal flux prior to 6.5 Ma. After 6.5 Ma, the Pb became stepwise more radiogenic and more similar to Equatorial Pacific seawater, reflecting the westward shift of spreading to the presently active East Pacific Rise (EPR). A second, previously unrecognized enhanced hydrothermal period occurred between 4.4 and 2.9 Ma, which reflects either off-axis hydrothermal activity in the Bauer Basin or a late-stage pulse of hydrothermal Pb from the then active, but waning Galapagos Rise spreading center. Hafnium isotope time-series of the same mixed hydrogenous-hydrothermal crust show invariant values over the past 7 Myr. Hafnium isotope ratios, as well as Nd isotope ratios obtained for this crust, are identical to that of hydrogenous Equatorial Pacific deep water crusts and clearly indicate that hydrothermal Hf, similar to Nd, does not travel far from submarine vents. Therefore, we suggest that hydrothermal Hf fluxes do not contribute significantly to the global marine Hf budget.

Zircon formation during fluid circulation in eclogites (Monviso, Western Alps): implications for Zr and Hf budget in subduction zones

The zircons from an eclogite and an enclosed eclogite-facies vein from the Monviso ophiolite (Western Alps) display contrasting chemical and morphologic features and document different stages of the evolution of the ophiolite. The zircons from the eclogite show a typical magmatic zoning and are enriched in heavy rare earth elements (HREEs) over middle rare earth elements (MREEs) and have an accentuated negative Eu anomaly, which indicates that the grains co-crystallised with plagioclase. These magmatic zircons document the formation of oceanic crust at 163 ± 2 Ma. In contrast, zircons from the vein contain inclusions of garnet, omphacite, and rutile, which indicate that they crystallised under eclogite-facies conditions. The vein zircons have Th/U ratios < 0.09, lack Eu anomalies, and are only weakly enriched in HREE with respect to MREE. These features are consistent with a garnet-bearing, plagioclase-free, i.e., eclogite-facies paragenesis. Vein zircons yield an age of 45 ± 1 Ma, which is evidence for Eocene subduction-zone metamorphism of the Monviso ophiolite. In the vein, the apparent coexistence of zircon, omphacite, and garnet permits the determination of a set of trace element distribution coefficients among these minerals at high pressure. This set of partitioning can demonstrate chemical equilibrium among these phases in rocks that show less clear evidence of textural equilibrium. In addition, zircon age can now be linked to sensors of metamorphic pressure-temperature conditions. The presence of zircon and rutile in the vein is another example of high field strength element (HFSE) mobility over short distances in aqueous fluids at eclogite-facies conditions. However, the concentrations of Zr and Hf in the aqueous fluid are estimated to be at least a factor of 10 less than primitive mantle values. Mass balance calculations demonstrate that zircon hosts > 95% of the bulk Zr, 90% of Hf, and ∼25% of U in the vein. Zircon is a residual phase in subducted basalts and sediments up to temperatures of at least 800 to 900 °C. Therefore, residual zircon in subducted crust, together with rutile, control the HFSE in liberated subduction zone fluids/melts and might be partly responsible for negative Zr and Hf anomalies in subduction zone magmas.

Multiple mantle sources during island arc magmatism: U–Pb and Hf isotopic evidence from the Kohistan arc complex, Pakistan

ABSTRACT This paper presents high‐precision U–Pb ages and initial Hf isotopic compositions of zircon from mafic to felsic rocks of the Kohistan Arc Complex, Pakistan. Three magmatic pulses tapping geochemically different reservoirs are distinguished. Partial melting of mantle with MORB‐type isotopic characteristics generated 99–92‐Ma‐old magmas. Plutonism around 85 Ma tapped a more fertile mantle source, most likely consisting of a &gt;600‐Ma‐old metasomatically enriched mantle, or of mantle contaminated by an old sedimentary component; 82‐Ma‐old felsic peraluminous dykes have MORB‐type isotopic compositions considered to be inherited from remelting earlier magmas in the deep base of the arc. The isotopic results demonstrate several and rather rapid changes in melt source region during arc development. They also show that there was subordinate continental influence and negligible importance of slab components for the Hf budget during the generation of the Kohistan Arc Complex.

Complex Sm-Nd and Lu-Hf isotope systematics in metamorphic garnets from the Isua supracrustal belt, West Greenland

Combined Sm-Nd and Lu-Hf isotope analyses of metamorphic garnets from the Earth’s oldest oceanic crustal sequence (the Isua supracrustal belt, West Greenland) yield errorchrons with apparent late Archean (2.8 Ga) crystallization dates. This contrasts with field and other geochronological evidence that link garnet growth to an early Archean (3.7 Ga) metasomatic-metamorphic event, but agrees more closely with the timing of a regional thermal overprint known to have affected both the Isua supracrustal belt and adjacent gneisses. Sm-Nd geochronological evidence presented here shows that the garnets were never reopened after garnet growth. The apparent partial reopening of the Sm-Nd isotope system within bulk garnets is instead explained by variable resetting of metamict allanite inclusions and their differing relative abundances within the garnet hosts. Allanite precipitated from metasomatic alteration fluids that percolated through the rocks during the emplacement of tonalite sheets. While light-rare-earth-element-rich allanite inclusions can affect the Sm-Nd system of bulk garnet, its low heavy-rare-earth element and Hf contents produce no measurable effect on the Lu-Hf system. Rather, the abundant common Hf in zircon, also present as inclusions in the garnets, affected the Hf budget to the extent of significantly lowering apparent Lu-Hf garnet ages. Whether the zircon inclusions are older (i.e., inherited) or contemporaneous (i.e., metasomatic) with the host garnets cannot be resolved with the present data. Despite the complications caused by inclusions in the garnets analyzed here, this study shows evidence for a metasomatic event at 3.7 Ga and a widespread resetting event at 2.3 Ga, but no evidence for a meaningful geologic event at 2.8 Ga. The 2.8 Ga Sm-Nd and Lu-Hf correlation lines obtained for the Isua garnets are interpreted as mixing lines between, respectively, metamict allanite and metamict zircon, both reset at 2.3 Ga, and garnet crystallized at 3.7 Ga. This study emphasizes the need for caution in the interpretation of Sm-Nd and Lu-Hf geochronological data involving garnets. Highly resistant inclusions, such as zircon, are unlikely to re-equilibrate with their host mineral during later tectono-metamorphic overprints and can severely bias parent-daughter element budgets. Likewise, metamictization of Th-U-rich inclusions (such as allanite and some zircons) within host minerals (in this case garnet) renders the inclusions increasingly prone to open-system behavior during later thermal events, leading to apparent initial isotopic disequilibrium between the inclusion phase and its less affected host. Finally, an initital εNd value at 3.7 Ga of −14 for garnets not containing allanite inclusions suggests the presence in the Isua area of very early differentiated crust.