Highly depleted Hadean mantle reservoirs in the sources of early Archean arc-like rocks, Isua supracrustal belt, southern West Greenland

Growing evidence from the accessible geological record reveals that crust-mantle differentiation on Earth started as early as 4.4 Ga. In order to assess the extent of early Archean mantle depletion, we obtained ¹⁷⁶Lu-¹⁷⁶Hf, ¹⁴⁷Sm-¹⁴³Nd, and high field strength element (HFSE) concentration data for the least altered, well characterized boninite-like metabasalts and associated metasedimentary rocks from the Isua supracrustal belt (southern West Greenland). The metasediments exhibit initial εHf₍₃₇₂₀₎ values from −0.7 to +1.5 and initial εNd₍₃₇₂₀₎ values from +1.6 to +2.1. Initial εHf₍₃₇₂₀₎ values of the least altered boninite-like metabasalts span a range from +3.5 to +12.9 and initial εNd₍₃₇₂₀₎ values from −0.3 to +3.2. These initial Hf-isotope ratios display coherent trends with SiO₂, Al₂O₃/TiO₂ and other relatively immobile elements, indicating contamination via assimilation of enriched components, most likely sediments derived from the earliest crust in the region. This model is also consistent with previously reported initial γOs₍₃₇₂₀₎ values for some of the samples. In addition to the positive εHf₍₃₇₂₀₎ values, the least disturbed samples exhibit positive εNd₍₃₇₂₀₎ values and a co-variation of εHf₍₃₇₂₀₎ and εΝd₍₃₇₂₀₎ values. Based on these observations, it is argued, that the most depleted samples with initial εHf₍₃₇₂₀₎ values of up to +12.9 and high ¹⁷⁶Lu/¹⁷⁷Hf of ∼0.05 to ∼0.09 tap a highly depleted mantle source with a long term depletion history in the garnet stability field. High precision high field strength element (HFSE) data obtained for the Isua samples confirm the contamination trend. Even the most primitive samples display negative Nb-Ta anomalies and elevated Nb/Ta, indicating a subduction zone setting and overprint of the depleted mantle sources by felsic melts generated by partial melting of eclogite. Collectively, the data for boninite-like metabasalts support the presence of strongly depleted mantle reservoirs as previously inferred from Hf isotope data for Hadean zircons and combined ¹⁴²Nd-¹⁴³Nd isotope data for early Archean rocks.     

Sulfur isotope studies in early Archaean sediments from Isua,West Greenland: Implications for the antiquity of bacterial sulfate reduction

The sulfur contents and sulfur isotope ratios (δ³⁴S) have been measured for samples collected from the Isua area of West Greenland in an effort to place narrower limits on the time of the rise of sulfate respirers during the Precambrian.The δ³⁴S values of the Isua sediments (3.7 × 10⁹ yr old) including the various facies of the banded iron-formations have their mean values close to zero %. (CDT) (±0.5%.) with a standard deviation of less than 1%.. This comes extremely close to the respective means yielded by the presumed tuffaceous amphibolites (+ 0.3 ± 0.9%.) and by the somewhat younger, between 3.1 and 3.7 ± 10⁹ yr, basaltic Ameralik dykes of the region (+ 0.6 ± 1.1%.).In view of the regional distribution of the Isua banded iron-formation sediments, the variety of environmental conditions under which the various facies were deposited and the complete absence of isotopic evidence for sulfate reducers, in contrast to the banded iron-formations of the middle Archaean (δ³⁴Svariesfrom ?20 to +20%.), it seems most unlikely that evidence for 'sulfate reducers' existed or will be found in other sediments of Isua age.The very small spread in δ³⁴S values for the Isua sediments is interpreted as due to minor fractionation during the passage of endogenic sulfur phases to their present sites of emplacement within the sedimentary succession.     

Nitrogen and argon isotopic signatures in graphite from the 3.8-Ga-old Isua Supracrustal Belt, Southern West Greenland

The problems involved with the interpretation of carbon isotopes as indicators for early life in highly metamorphosed early Archean rocks have prompted the search for additional chemical and isotopic biomarkers. Here we report an attempt to identify the origin of carbonaceous matter in the 3.8 Ga old Isua Supracrustal Belt in southern West Greenland by measuring the concentration and isotopic composition of a trapped nitrogen component. Stepped-combustion/pyrolysis-mass spectrometry of carbonaceous matter in several rock samples revealed three different reservoirs of trapped nitrogen: (1) nitrogen associated with a very small amount of reactive carbonaceous material, (2) nitrogen intercalated in graphite, correlated with intercalated radiogenic argon, (3) nitrogen strongly retained at defects or chemically bound in the graphite structure. The δ¹⁵N of nitrogen associated with reactive carbonaceous matter (ca. +6‰) overlaps with that of average Phanerozoic sedimentary organic matter, and is believed to be part of nonindigenous postmetamorphic biologic material. In situ Raman spectroscopy confirmed the high degree of crystallinity of the metamorphosed indigenous carbonaceous material, and this material is further referred to as graphite. Graphite interpreted as epigenetic (associated with Mg,Mn-siderite in metacarbonates) contains a very small strongly retained nitrogen component with a low δ¹⁵N ratio (−3 to −1‰). This range overlaps with values that are typically found in Archean kerogens, but also those of a metamorphically emplaced inorganic basaltic source. Geological constraints suggest that this graphite incorporated nitrogen from surrounding metabasaltic rocks. Graphite interpreted as syngenetic and biogenic found in a turbidite deposit is relatively similar to this Mg,Mn-siderite-derived graphite, based on degree of graphite crystallinity, amount of trapped radiogenic argon, low nitrogen concentration and δ¹⁵N signature. We conclude that nitrogen concentration and its isotope ratio in graphite cannot be used conclusively as a biomarker in these rocks from the highly metamorphosed Isua Supracrustal Belt.     

Meta-igneous (non-gneissic) tonalites and quartz-diorites from an extensive ca. 3800 Ma terrain south of the Isua supracrustal belt, southern West Greenland: constraints on early crust formation

In the Itsaq Gneiss Complex south of the Isua supracrustal belt (West Greenland) some areas of early Archaean tonalite and quartz-diorite are non-gneissic, free of pegmatite veins, and in rarer cases are undeformed with relict igneous textures and hence were little modified by heterogeneous ductile deformation under amphibolite facies conditions in several Archaean events. Such well-preserved early Archaean rocks are extremely rare. Tonalites are high Al, and have bulk compositions close to experimental liquids. Trace element abundances and modelling suggest that they probably originated as melts derived from basaltic compositions at sufficiently high pressures to require residual garnet + amphibolites ± clinopyroxene in the source. The major element characteristics of the quartz-diorites suggest these were derived from more mafic magmas than the tonalites, and underwent either igneous differentiation or mixing with crustal material. As in modern arc magmas, high relative abundances of Sr, Ba, Pb, and alkali elements cannot be generated simply from a basaltic source formed by large degrees of melting of a depleted mantle. This may indicate an important role for fluids interacting with mafic rocks in generating the earliest preserved continental crust. The high Ba/Th, Ba/Nb, La/Nb and low Nb/Th, Ce/Pb, and Rb/Cs ratios of these tonalites are also observed in modern arc magmas. SHRIMP U-Pb zircon geochronology was undertaken on seven tonalites, one quartz-diorite, a thin pegmatitic vein and a thin diorite dyke. Cathodoluminescence images show the zircon populations of the quartz-diorite and tonalites are dominated by single-component oscillatory-zoned prismatic grains, which gave ages of 3806 ± 5 to 3818 ± 8 Ma (2σ) (quartz-diorite and 5 tonalites) and 3795 ± 3 Ma (1 tonalite). Dating of recrystallised domains cutting oscillatory-zoned zircon indicates disturbance as early as 3800–3780 Ma. There are rare ca. 3600 Ma and 3800–3780 Ma (very high U and low Th/U) ≤ 20 μm wide partial overgrowths on the prismatic grains. Given likely Zr-undersaturation of precursor melts and evidence of zircon recrystallisation and metamorphic regrowth as early as 3800–3780 Ma, the age determinations on the prismatic oscillatory-zoned zircon populations give the igneous crystallisation age of the tonalite and quartz-diorite protoliths. When the coherency of the geochemistry is considered, these samples represent the best preserved suites of ca. 3800 Ma felsic igneous rocks yet documented. Received: 1 December 1998 / Accepted: 23 July 1999     

Influence of contamination on banded iron formations in the Isua supracrustal belt,West Greenland: Reevaluation of the Eoarchean seawater compositions

Banded Iron Formations(BIFs) are chemical sediments, ubiquitously distributed in the Precambrian supracrustal belts; thus their trace element compositions are helpful for deciphering geochemical evolution on the Earth through time. However, it is necessary to elucidate factors controlling the whole-rock compositions in order to decode the ancient seawater compositions because their compositions are highly variable. We analyzed major and trace element contents of the BIFs in the 3.8-3.7 Ga Isua supracrustal belt(ISB), southern West Greenland. The BIFs are petrographically classified into four types:Black-,Gray-, Green-and White-types, respectively. The Green-type BIFs contain more amphiboles, and are significantly enriched in Co, Ni, Cu, Zn, Y, heavy rare earth element(HREE) and U contents. However,their bulk compositions are not suitable for estimate of seawater composition because the enrichment was caused by secondary mobility of metamorphic Mg, Ca and Si-rich fluid, involvement of carbonate minerals and silicate minerals of olivine and pyroxene and/or later silicification or contamination of volcanic and clastic materials. The White-type BIFs are predominant in quartz, and have lower transition element and REE contents. The Gray-type BIFs contain both quartz and magnetite. The Black-type BIFs are dominated by magnetite, and contain moderate to high transition element and REE contents. But,positive correlations of V, Ni, Zn and U contents with Zr contents suggest that involvement of detrital,volcanic and exhalative materials influences on their contents. The evidence for significant influence of the materials on the transition element contents such as Ni in the BIFs indicates the transition element contents in the Archean ocean were much lower than previously estimated. We reconstructed secular variations of V,Co, Zn and U contents of BIFs through time, which show Ni and Co contents decreased whereas V, Zn and U contents increased through time. Especially, the Ni and Co contents drastically decreased in the Mesoarchean rather than around the Great Oxidation Event. On the other hand, the V,Zn and U contents progressively increased from the Mesoarchean to the Proterozoic. Stratigraphical trends of the BIFs show increase in Y/Ho ratios and decrease in positive Eu anomaly upwards, respectively. The stratigraphic changes indicate that a ratio of hydrothermal fluid to seawater component gradually decrease through the deposition, and support the Eoarchean plate tectonics, analogous to the their stratigraphic variations of seafloor metalliferous sediments at present and in the Mesoarchean.     

鞍山-本溪地区条带状铁矿的Fe同位素特征及其对成矿机理和地球早期海洋环境的制约

本文报道了鞍山-本溪地区晚太古代条带状铁建造的主量元素、微量元素、稀土元素和Fe同位素的分析结果.结果显示:铁矿主要由Fe2O3T和SiO2组成,具有较低的Al2O3和TiO2含量;微量元素含量和稀土总量均较低;经页岩标准化的稀土元素配分模式呈现轻稀土亏损、重稀土富集;具有明显的La、Eu、Y的正异常;较高的Y/Ho比值.这些特征均表明鞍山-本溪地区条带状铁矿是由极少碎屑物质加入的化学沉积岩,成矿物质主要来源于海底热液的贡献.相对于标准物质IRMM-014,条带状铁矿石的Fe同位素组成最突出的特征是均为正值,这是由于二价铁溶液经部分氧化和沉淀形成富集重铁同位素的三价铁氧化物或氢氧化物的结果,且沉淀程度的不同是控制Fe同位素组成变化的重要因素.条带状铁矿无明显的Ce负异常和Fe同位素组成为正值的特征暗示了铁矿沉淀时的海水为低氧逸度环境.     

Metamorphic fluid flow in the northeastern part of the 3.8-3.7 Ga Isua Greenstone Belt (SW Greenland): A re-evalution of fluid inclusion evidence for early Archean seafloor-hydrothermal systems

Fluid inclusions in quartz globules and quartz veins of a 3.8-3.7 Ga old, well-preserved pillow lava breccia in the northeastern Isua Greenstone Belt (IGB) were studied using microthermometry, Raman spectrometry and SEM Cathodoluminescence Imaging. Petrographic study of the different quartz segregations showed that they were affected by variable recrystallization which controlled their fluid inclusion content. The oldest unaltered fluid inclusions found are present in vein crystals that survived dynamic and static recrystallization. These crystals contain a cogenetic, immiscible assemblage of CO₂-rich (+H₂O, +graphite) and brine-rich (+CO₂, +halite, +carbonate) inclusions. The gas-rich inclusions have molar volumes between 44.8 and 47.5 cm³/mol, while the brine inclusions have a salinity of ∼33 eq. wt% NaCl. Modeling equilibrium immiscibility using volumetric and compositional properties of the endmember fluids indicates that fluid unmixing occurred at or near peak-metamorphic conditions of ∼460 °C and ∼4 kbar. Carbonate and graphite were precipitated cogenetically from the physically separated endmember fluids and were trapped in fluid inclusions.In most quartz crystals, however, recrystallization obliterated such early fluid inclusion assemblages and left graphite and carbonate as solid inclusions in recrystallized grains. Intragranular fluid inclusion trails in the recrystallized grains of breccia cementing and crosscutting quartz veins have CO₂-rich assemblages, with distinctly different molar volumes (either between 43.7 and 47.5 cm³/mol or between 53.5 and 74.1 cm³/mol), and immiscible, halite-saturated H₂O-CO₂-NaCl(-other salt) inclusions. Later intergranular trails have CH₄-H₂ (X_H2 up to ∼0.3) inclusions of variable density (ranging from 48.0 to >105.3 cm³/mol) and metastable H₂O-NaCl(-other salt?) brines (∼28 eq. wt% NaCl). Finally, the youngest fluid inclusion assemblages are found in non-luminescent secondary quartz and contain low-density CH₄ (molar volume > 105.33 cm³/mol) and low-salinity H₂O-NaCl (0.2-3.7 eq. wt% NaCl). These successive fluid inclusion assemblages record a retrograde P-T evolution close to a geothermal gradient of ∼30 °C/km, but also indicate fluid pressure variations and the introduction of highly reducing fluids at ∼200-300 °C and 0.5-2 kbar. The quartz globules in the pillow fragments only contain sporadic CH₄(+H₂) and brine inclusions, corresponding with the late generations present in the cementing and crosscutting veins. We argue that due to the large extent of static recrystallization in quartz globules in the pillow breccia fragments, only these relatively late fluid inclusions have been preserved, and that they do not represent remnants of an early, seafloor-hydrothermal system as was previously proposed.Modeling the oxidation state of the fluids indicates a rock buffered system at peak-metamorphic conditions, but suggests a change towards fluid-graphite disequilibrium and a logf_H2/f_H2O above the Quartz-Fayalite-Magnetite buffer during retrograde evolution. Most likely, this indicates a control on redox conditions and on fluid speciation by ultramafic rocks in the IGB.Finally, this study shows that microscopic solid graphite in recrystallized metamorphic rocks from Isua can be deposited inorganically from a fluid phase, adding to the complexity of processes that formed reduced carbon in the oldest, well-preserved supracrustal rocks on Earth.     

Carbon isotope geochemistry of the 3.7 × 109-yr-old Isua sediments,West Greenland: implications for the Archaean carbon and oxygen cycles

One hundred and twenty-four carbonate samples from the meta-sedimentary sequence of the 3.7 × 10⁹ yr old Isua supracrustal belt (W-Greenland) have yielded a δ¹³C_carb average of ?2.5 ± 1.7%. vs PDB and a δ¹⁸O_carb average of +13.0 ± 2.5%. vs SMOW. The oxygen mean comes fairly close to the averages of other early Precambrian carbonates. The carbon average, however, is some 2%. more negative than those of younger marine carbonates. In terms of a simple terrestrial ¹³C mass balance, if δ¹³C_carb values are original sedimentary values, this more negative δ¹³C average would imply a considerably smaller $\text{C}{}_{\mathrm{org}}\text{C}{}_{\mathrm{carb}}$ ratio in the sedimentary shell during Isua times, and would thus support the concept of a gradual buildup of a sedimentary reservoir of organic carbon during the early history of the Earth. Since, however, the Isua supracrustal rocks have experienced amphibolite-grade metamorphism, which in other areas has been shown to lower δ¹³C_carb values, it is most likely that the original values of these rocks were approx 0%.. This indicates that C_orx and C_carb were present in the ancient carbon reservoir in about ‘modern’ proportions. Unless this early stabilization of the terrestrial carbon cycle in terms of a constant partitioning of carbon between the reduced and oxidized species is shown to have been caused by some inorganic geochemical process, a considerably earlier start of chemical evolution and spontaneous generation of life must be considered than is presently accepted.     

Major element distribution in Archean banded iron formation (BIF): influence of metamorphic differentiation

The Archean (2.8 Ga) Banded Iron Formation (BIF) of the Bell Lake region of Yellowknife greenstone belt, Canada is recrystallized to metamorphic assemblages of the amphibolite facies. This BIF is characterized by centimetre‐scale Fe‐rich and Si‐rich mesobands. In the Si‐rich mesobands, thin layers of magnetite microbands are developed in a quartz matrix. The Fe‐rich mesobands are composed mainly of Ca‐amphibole (hornblende), Fe–Mg amphibole (grunerite), and magnetite. The metamorphic foliation locally cuts across the mesoband boundaries, indicating the mesobanding was formed prior to peak metamorphism. Variations in mineral modal proportions between Fe‐rich mesobands and microbands are diagnostic of depositional compositional differences between beds. Micro‐X‐ray fluorescence imaging reveals metamorphic differentiation within Fe‐rich mesobands, with segregation of Fe–Mg amphibole, and the incompatible element Mn is concentrated at the margins of the Fe‐rich mesobands during the amphibole‐forming reactions. Ti was relatively immobile during metamorphic segregation and its distribution provides a record of the original structures in the Fe‐rich mesobands.     

Deserpentinization and high-pressure(eclogite-facies) metamorphic features in the Eoarchean ultramafic body from Isua,Greenland

Discontinuous chains of ultramafic rock bodies form part of the 3800–3700 Ma Isua Supracrustal Belt(ISB),hosted in the Itsaq Gneiss Complex of southwestern Greenland.These bodies are among the world’s oldest outcrops of ultramafic rocks and hence an invaluable geologic record.Ultramafic rocks from Lens B in the northwestern limb of ISB show characteristics of several stages of serpentinization and deserpentinization forming prograde and retrograde mineral assemblages.Ti-rich humite-group minerals such as titanian chondrodite(Ti-Chn)and titanian clinohumite(Ti-Chu)often occur as accessory phases in the metamorphosed ultramafic rocks.The Ti-rich humite minerals are associated with metamorphic olivine.The host olivine is highly forsteritic(Fo96-98)with variable Mn O and Ni O contents.The concentrations of the rare-earth elements(REE)and high-field strength elements(HFSE)of the metamorphic olivine are higher than typical mantle olivine.The textural and chemical characteristics of the olivine indicate metamorphic origin as a result of deserpentinization of a serpentinized ultramafic protolith rather than primary assemblage reflecting mantle residues from high-degrees of partial melting.The close association of olivine,antigorite and intergrown Ti-Chn and Ti-Chu suggests pressure condition between$1.3–2.6 GPa within the antigorite stability field(<700°C).The overall petrological and geochemical features of Lens B ultramafic body within the Eoarchean ISB indicate that these are allochthonous ultramafic rocks that recorded serpentine dehydration at relatively lower temperature and reached eclogite facies condition during their complex metamorphic history similar to exhumed UHP ultramafic rocks in modern subduction zone channels.     

Sm-Nd, Lu-Hf and Pb-Pb signatures of gneisses and granitoids from the La Grande belt: extent of late Archean crustal recycling in the northeastern Superior Province, Canada

Sm-Nd, Lu-Hf and Pb-Pb isotopic signatures were determined for gneisses and felsic plutons of the La Grande granite-greenstone and the Nemiscau metasedimentary belts of Canada. The northern part of the La Grande belt exposes gneisses of the Langelier complex formed between ca. 2.8 and 2.9 Ga. The gneisses yielded εNd_(T) values between −2 and +1, εHf_(T) between −1 and +3, initial ²⁰⁷Pb/²⁰⁴Pb ratios of ∼14.9, higher than the value of 14.6 derived from the Stacey-Kramers growth curve, and crustal extraction ages ≥3.0 Ga. Modeling shows that the syn- to late-tectonic intrusions of granitoid rocks record at least 20%, and up to 40%, recycling of this gneissic basement. The southern part of the La Grande belt, where no basement gneisses are exposed, records lower proportions (5-20%) of this crustal end-member. In both parts of the La Grande belt, the post-tectonic plutons record the largest proportion of recycled crust, likely related to southeastward thrusting events in the Superior craton, crustal thickening and concomitant partial melting.The La Grande plutons have isotopic signatures more radiogenic than those of similar intrusions that formed concurrently, to the south, in the Abitibi greenstone belt. This reflects an ancient crust environment for the former vs. an oceanic setting for the latter. Mantle reservoirs with a protracted history of incompatible element depletion were present beneath the whole eastern Superior Province, in the late Archean.     

Sources of Archean sanukitoids (High-Mg subalkaline granitoids) in the Karelian craton: Sm-Nd and Rb-Sr isotopic-geochemical evidence

The Sm-Nd systematics of sanukitoids with an age of 2715–2740 Ma in the Western, Eastern, and Central domains of the Karelian craton with various crustal evolutionary histories indicates that the mafic and acid rocks of the sanukitoid series were derived from two contrasting sources: enriched lithospheric mantle and lower crust. The basic sanukitoids of the Western domain were derived from the mantle enriched long before its melting [?_Nd(2715) = ?0.48 ± 0.22]. The source of the acid magmas was the young juvenile crust of TTG composition [?_Nd(2715) increases to +1.2]. The mantle source of mafic sanukitoids in the Eastern domain was enriched shortly before melting [?_Nd(2740) = +1.58 ± 0.01], whereas the acid melts came from an ancient crustal source [?_Nd(2740) decreases to ?3.0]. For sanukitoids in the Central domain, the time span between the enrichment of the mantle source and its melting was the shortest [?_Nd(2725) = +2.05 ± 0.15], and the contribution of the juvenile TTG crust was insignificant [?_Nd(2725) deceases to +1.7]. The variations in the isotope characteristics of the acid members of the sanukitoid series are consistent with the known age heterogeneity of the crust of the domains. The lateral isotopic-geochemical heterogeneity of the lithospheric mantle source of the sanukitoids is thought to have been related to its two-stage reworking (at 3.2 and 2.8–2.9 Ga) under the effect of TTG granitoids, which are regarded as the melting products of the subducted oceanic crust. The sanukitoids provide information on the geochemical structure of the Archean lithosphere, which is reflected in Archean crust-building processes. The Rb-Sr isotope system of the Neoarchean sanukitoids underwent transformations on the mineralogical scale and within small massifs in the course of at least two Paleoproterozoic tectono-thermal events. A trace of the event at ～2.1 Ga is left in the Rb-Sr system of monomineralic fractions from a weakly deformed syenite of the sanukitoid series in the Central Domain. Later event (～1.7 Ga) was recorded in the minerals of the Teloveis sanukitoid massif, which hosts a gold mesothermal deposit in the Western domain. Monomineralic fractions of muscovite and biotite from the wall-rock metasomatites and of plagioclase, microcline, and biotite from metasomatites away from the orebodies yield isochron ages of 1719 ± 60 and 1717 ± 27 Ma. This age of the metasomatic alterations of the Neoarchean sanukitoids is able to explain the broad and unsystematic variations in the Rb-Sr isotope-geochemical characteristics of these rocks. Our data on the Paleoproterozoic age of the mesothermal gold ore mineralization at the Teloveis deposit provide additional lines of evidence for the complex tectonic and metallogenic evolution of the Karelian GGT in the Early Precambrian.     

Hydrothermal-metasomatic and tectono-metamorphic processes in the Isua supracrustal belt (West Greenland): a multi-isotopic investigation of their effects on the earth’s oldest oceanic crustal sequence

Despite superimposed metamorphic overprinting and metasomatic alterations, primary volcanic features remain preserved in low-strain domains of mafic volcanic sequences in the western Isua supracrustal belt (ISB, West Greenland). These basaltic successions represent the hitherto oldest known fragments of oceanic crust on Earth. Early Archean metasomatic fluids, rich in light rare earth elements (LREE), Th, U, Pb, Ba, and alkalies, invaded the supracrustal package and distinctively altered the basaltic sequences. Field relationships, source characteristics traced by Pb isotopes, and geochronological results provide indications that these fluids were genetically related to the emplacement of tonalite sheets into the ISB between 3.81 and 3.74 Ga ago. Subsequent early Archean metamorphism homogenized the mixed primary and metasomatic mineral parageneses of these metavolcanic rocks. Allanite occurs as the most characteristic and critical secondary metasomatic-metamorphic phase and is developed in macroscopically discernible zones of increased metsomatic alteration, even in domains of low strain. Because of its high concentration of LREE, Th, and U, this secondary mineral accounts for much of the disturbances recorded by the Sm-Nd and Th-U-Pb isotope systematics of the pillowed metabasalts.The supracrustal sequences were tectono-metamorphically affected to varying degrees during a late Archean, ∼2.6- to 2.8-Ga-old event, also recognized in the adjacent gneiss terranes of the Isuakasia area. The degree to which bulk rocks were isotopically reequilibrated is directly dependent on the different relative contributions of allanite-hosted parent-daughter elements to the overall whole-rock mass budget of the respective isotope systems. Although low-strained (initially only weakly metasomatized) pillow basalts remained more or less closed with respect to the U-Pb and Rb-Sr systems since ∼3.74 Ga, the Sm-Nd system appears to have been partially opened on a whole-rock scale during the late Archean event. This diversified behavior of the whole-rock isotope systems with respect to late Archean overprinting is explained by the combination of mass budget contributions of the respective elements added during metasomatism and the partial opening of metasomatic macroenvironments during late Archean recrystallization processes with associated renewed fluid flow. In reactivated zones of high strain, where primary metasomatic alteration is most prominently developed, late Archean partial resetting also of the U-Pb isotope system on a whole-rock scale occurred. This is consistent with an apparent late Archean age of kyanite, which initially crystallized during the early Archean metamorphism. Its age is controlled by the U-Pb systematics of allanite inclusions, which have exchanged their isotopic properties during the tectono-metamorphic event that overprinted the oceanic crustal sequence at Isua more than 1000 myr later.These results underline the need for care in the interpretation of whole-rock geochemical data from polymetamorphic rocks in general, and from the Isua oceanic crustal sequences in particular, to constrain isotopic models of early Earth’s evolution. Likewise, this study cautions against the indiscriminate use of geochemical data of metavolcanic rocks from Isua to infer models for geotectonic settings relevant for their formation.     

Alteration and metamorphism of Amitsoq gneisses from the Isukasia area,West Greenland: Recommendations for isotope studies of the early crust

Early Archaean gneisses (3400–3700 Ma) in the Isukasia area of West Greenland have been subjected to a series of local and regional metamorphic processes. Metasomatic alteration accompanied the intrusion of the early Archaean white gneisses (~3600 Ma) into the grey gneisses (~3700 Ma), and resulted in local formation of altered rocks. Pb-Pb isotope results on whole rock and feldspar from the gneisses reveal a major rearrangement of Pb isotopes at about 2600 Ma together with some local third stage Pb changes at a later time. This 2600 Ma event is also shown by Rb-Sr data for phengites in the ~3400 Ma Pegmatitic gneiss sheets and can be correlated with metamorphism accompanying the intrusion of a late Archaean pegmatite (~2600 Ma) swarm. Local hydrothermal alteration by fluids emanating from Proterozoic faults and fractures is petrographically recognised in and near major faults and lithological boundaries. This fault-controlled alteration, though only locally significant, may correlate with low grade thermal metamorphism reflected in a 1600 Ma Rb-Sr mineral isochron on biotites from both altered and unaltered gneisses. Oxygen isotope results show that this alteration probably was associated with influx of a low-δ¹⁸O fluid, perhaps meteoric water. Selection of the least altered Amitsoq gneisses can be made on the basis of petrographic and field criteria, and furnishes the best material to study original geochemical and isotopic systematics in these early Archaean rocks.     

Implications of Pb isotope signatures of rocks and iron oxide Cu-Au ores in the Candelaria-Punta del Cobre district,Chile

Lead isotope ratios of ores of the Candelaria-Punta del Cobre iron oxide Cu-Au deposits and associated Early Cretaceous volcanic and batholithic rocks have been determined. For the igneous rocks, a whole-rock acid attack technique based on the separate analyses of a leachate and the residual fraction of a sample was used. The lead isotope systematics of leachate–residue pairs are significantly different for unaltered and altered igneous rocks of the Candelaria-Punta del Cobre district. Residues of unaltered igneous rocks likely represent the common lead. In contrast, residues of all the altered igneous rocks except two samples have higher Pb isotope ratios than those of unaltered magmatic rocks and cannot represent common lead. We suggest that this is a result of the hydrothermal alteration suffered by these rocks and that the common lead composition of the altered igneous (volcanic and plutonic) rocks must have been similar to that of the unaltered batholith rocks. The conclusion that the altered volcanic rocks originally had a similar common lead isotope composition as the batholith is consistent with geological and geochemical arguments (e.g., setting, regional geologic evolution, ages and relative distribution of volcanic and intrusive rocks, magmatic affinities), which indicate that these rocks were derived from similar Early Cretaceous parent magmas. The modification of the leachate–residue pair lead isotope systematics of most altered igneous rocks is consistent with a selective removal of lead and uranium from these rocks by an oxidized hydrothermal fluid. The result of the hydrothermal leaching has been to alter magmatic rocks in a way that (1) their leachable fraction is presently a mix of common lead similar to that of the ore event and of radiogenic lead evolved from a source with a consistently high Th/U, and that (2) their residual fraction has less common lead than unaltered rocks. The outcrop area with altered volcanic rocks displaying anomalously high lead isotope ratios extends over 25 km along the eastern margin of the batholith. Since lead of the ores in the Candelaria-Punta del Cobre district has the same isotopic composition as the common lead of unaltered magmatic rocks of the area, the lead isotope data are consistent with a derivation of the ore lead (and by inference of other metals like Cu) both directly from a magmatic fluid exsolved during crystallization of the batholith and/or from hydrothermal leaching of the volcanic rocks originally having similar isotopic compositions as the batholith.Editorial handling: B. Lehmann     

Recognizable primary volcanic and sedimentary features in a low-strain domain of the highly deformed, oldest known (≈ 3.7–3.8 Gyr) Greenstone Belt, Isua, West Greenland

A low-strain domain has been identified in the metamorphosed, mostly highly deformed volcanic and sedimentary rocks of the early Archaean Isua supracrustal belt. This domain contains well-preserved volcanic and sedimentary features, including basaltic pillow lavas, pillow breccia, heterogeneous volcanic breccia, amygdules in metabasalt, and polymict conglomerate dominated by recrystallized chert and volcanic clasts. The low-strain domain is bounded by highly deformed rocks mostly derived from basalt, chert, and banded iron formation. These discoveries demonstrate that some primary features have escaped the pervasive metasomatism dominant in other parts of the belt and, furthermore, strengthen the characterization of the Isua supracrustals as a typical greenstone belt.     

Provenance change in the Irkutsk coal basin during the early and middle Jurassic: Geochemical and Sm-Nd isotope evidence

On the basis of the recently accepted chronostratigraphic chart, Jurassic sedimentation in the Irkutsk coal basin took place over a short time interval (~23 My), from the Pliensbachian (~191 Ma) to the Aalenian (~170 Ma). In this study, we present geochemical and Sm-Nd isotope data for sedimentary rocks of the Prisayan and Kuda formations and those in the upper course of the Angara River, which were deposited over an even shorter time interval (from ~174 to 170 Ma), as indicated by new data on biostratigraphy. Our results suggest that a greater contribution from Transbaikalia compared to that from the Siberian Platform during sediment deposition in the Irkutsk coal basin may reflect the onset of mountain building in Transbaikalia and reorganization of the river drainage network during the Middle Jurassic.     

Geogenic and anthropogenic lead isotope signatures in the urban environment of Natal (NE-Brazil)

In this study the effect of anthropogenic emissions on the lead isotopic composition of sediments from the Potengi-Jundiai river system near the fast growing city of Natal, NE-Brazil, is investigated. The lead isotope signatures of sediments from the region of Natal were measured by ICP QMS and can be discussed in terms of three different end members of lead. Two geogenic lead endmembers can be distinguished and also be spatially separated, as higher lead isotope ratios occur in the vicinity of the town of Macaiba while the lead isotope ratios decrease towards the city of Natal and the mouth of the estuary. Proterozoic rocks of different age are potential lead sources as Paleoproterozoic rocks occur in the catchment of Jundiai river and younger, Neoproterozoic rocks predominate towards the mouth of the river. The lead isotope signatures of the anthropogenically affected samples deviate from the signatures of the unaffected samples indicating the existence of a third, anthropogenic source of lead. This source represents the lead isotope signature of anthropogenic emitters like waste- and coal-combustion which is also revealed by other geochemical studies conducted in Brazil.     

Sm-Nd isotope systematics in garnet from different lithologies (Eastern Alps): age results, and an evaluation of potential problems for garnet Sm-Nd chronometry [Chem. Geol. 185 (2002) 255-281]

Interpretation of Sm-Nd garnet ages is frequently impaired by one of the following restrictions: (a) high-LREE inclusions, (b) isotopic disequilibrium, and (c) the uncertainty about the closure temperature. These issues are addressed by way of an evaluation of garnet Sm-Nd data from different rock types of the Austroalpine basement units, Eastern Alps, including metabasic eclogites, mica schist and paragneiss, metapegmatite and metagranite.Nd concentration in handpicked garnet varies between 0.021 and 23.1 ppm in metabasites, 0.49 and 17.4 ppm in metapelites and between 0.024 and 4.6 ppm in metapegmatites and metagranites. The overall range of ¹⁴⁷Sm/¹⁴⁴Nd is 0.15-2.5 in garnet from metabasites, 0.12-3.03 in metapelite garnet and 0.66-7.21 in Mn-rich garnet from metapegmatites and metagranites. A clear negative correlation between Nd concentration and Sm/Nd is observed in garnets from all these lithologies. Therefrom, it is concluded that even optically “clean” garnet separates may contain high-LREE microinclusions, such as epidote-allanite, zoisite, apatite, sphene, monazite or zircon. However, very low Nd concentrations correlated with low Sm/Nd as well as high Nd concentrations (>5 ppm) correlated with fairly high Sm/Nd ratios (0.8) have also been observed. Apart from replicate analyses within as well as between samples with a common PT-history, leaching experiments are a useful technique to elucidate any distorting influence of unequilibrated inclusions on the garnet age, especially if the observed Sm/Nd ratio is low (<0.5). Leaching of garnet separates with HCl (2.5, 5.8 M) produces no obvious element fractionation, but may improve Sm/Nd, and hence age precision, considerably. Isotopic disequilibrium between garnet and other matrix minerals is observed preferentially in basic eclogites, derived from gabbroic precursors.Sm-Nd garnet analysis allows the recognition of several distinct garnet-forming events in the Eastern Alps.(a) A Variscan high-P event is documented in metabasites from the northern-central Ötztal basement around 360-350 Ma, whereas garnet from sillimanite-bearing gneisses dates the Variscan thermal peak in the western part of the same subunit around 345-330 Ma.(b) A long-lived, Permian to Triassic event (285-225 Ma), correlated with crustal extension and low-P metamorphism, is documented by spessartine-rich garnet from metapegmatites as well as almandine-rich garnet cores from mica schist.(c) Age data of garnet from eo-Alpine (Cretaceous) deeply subducted rocks of the southern/eastern Austroalpine units are related to near-peak PT, eclogite- to amphibolite-facies metamorphic conditions (peak: 2 GPa/685 °C), and/or incipient isothermal decompression, due to fast, tectonically driven exhumation (110/100-85 Ma). At cooling rates of 20-30 °C/Ma (exhumation rates: 3-5 km/Ma), the Sm-Nd closure temperature (T_c) for mm-sized garnet in these rocks is estimated at 650-680 °C.