Distribution of high field strength elements (Y, Zr, REE, Hf, Ta, Th, U) in adjacent magnetite and chert bands and in reference standards FeR-3 and FeR-4 from the Temagami iron-formation, Canada, and the redox level of the Neoarchean ocean

Adjacent magnetite and chert bands and reference standards FeR-3 and FeR-4 from the Neoarchean Temagami iron-formation (IF) show shale-normalized rare earth and yttrium (REY) patterns with low Nd/Yb ratios and positive Eu, Gd and Y anomalies, indicating that they formed as marine chemical sediments. In contrast to previous claims, none of the samples shows any Ce anomaly, indicating the absence of oxidative Ce-REY decoupling and arguing against oxic conditions in the wider vicinity of the Neoarchean “Temagami seabasin”. The distribution of Zr, Hf and Ta yields Zr/Hf and Hf/Ta ratios that differ from those of chondrites, average upper continental crust and local shales, suggesting that the Temagami IF is the only case observed so far in which a significant fraction of these elements is non-detrital but sourced from seawater. If Neoarchean seawater was characterized by Zr/Hf and Hf/Ta ratios similar to those of modern seawater these ratios point towards preferential scavenging of Hf over Zr and Ta, as is typical of the modern ocean. Similar to the 2.9 Ga old Mozaan IF in the Pongola Supergroup, South Africa, the Temagami IF shows low Th/U ratios that differ from those of the respective local shales and from that of average upper continental crust. Decoupling of U and Th results from U⁴⁺ oxidation in the Earth's surface system and fractionated Th/U ratios in these marine chemical sediments are, therefore, at odds with the lack of Ce anomalies. This suggests a different redox-sensitivity of the two paleo-redox-proxies Th–U and Ce-REY and demonstrates that the Temagami IF and the Mozaan IF warrant further study of other paleo-redox-proxies.     

Chemical evolution of seawater in the Transvaal Ocean between 2426 Ma (Ongeluk Large Igneous Province) and 2413 Ma ago (Kalahari Manganese Field)

Drill core and outcrop samples of pure marine chemical sediments (banded iron formation (BIF), manganese formation (MnF), jaspilites, lutites, and cherts) from the transition of the ~2426 Ma old Ongeluk Formation into the 2413 Ma old Hotazel Formation, Transvaal Supergroup, South Africa, reveal remarkable changes of seawater chemistry in the Transvaal Ocean. Similar to pre-Ongeluk chemical sediments, the shale-normalized rare earths and yttrium (REY_SN) patterns of jaspilites intercalated with the volcanic rocks of the Ongeluk large igneous province and directly overlying cherts do not show positive Eu_SN anomalies, indicating that high-temperature (>250 °C) hydrothermal fluids did not contribute significantly to the REY budget of ambient waters. However, a 10 cm drill core section in the lower Hotazel Formation is characterized by conspicuous positive Eu_SN anomalies, revealing temporary inflow of water masses strongly affected by high-temperature hydrothermal fluids. After this short episode, the REY_SN pattern of Transvaal seawater returned to that of pre-Ongeluk times, showing heavy REY_SN enrichment, positive La_SN, Gd_SN and Y_SN anomalies, but no Ce_SN or Eu_SN anomalies. Higher up in the stratigraphy, the Hotazel Formation shows negative Ce_SN anomalies in some of the lutites, BIFs and MnFs, reflecting Ce depletion in ambient seawater. All Hotazel lutite, BIF, and MnF samples studied show unradiogenic εNd_(t) values (−0.5 ± 0.2 to −2.4 ± 0.2), indicating a mostly continental REY source. The REY distribution and Nd isotope data combined suggest that oxidative terrestrial weathering of this continental crustal source supplied most of the dissolved REY to local “Transvaal seawater”. Precipitation of the Hotazel lutites, BIFs and MnFs with negative Ce_SN anomalies, therefore, suggests that oxic conditions prevailed on the Kaapvaal Craton and in Hotazel seawater already at ~2.413 Ga, i.e. 80 m.y. before the disappearance of mass-independent sulfur isotope fractionation (MIF-S) that defines the Great Oxidation Event at ~2.33 Ga.     

Do Archean chemical sediments record ancient seawater rare earth element patterns?

Rare earth elements (REE) concentrations of Archean and Proterozoic chemical sediments are commonly used as proxies to study secular trends in the geochemistry of Precambrian seawater. In addition, similarities in the REE signatures of Archean chemical sediments and modern seawater have led researchers to argue that some Archean rocks originated as biochemical precipitates (i.e., microbial carbonates) in shallow marine (e.g., peritidal) environments. However, terrestrial waters, including river water and groundwater, also commonly exhibit REE fractionation patterns that resemble modern seawater. Here, we present the seawater-like REE data for groundwaters from central México as additional evidence that these patterns are not unique to the marine environment. The shale-normalized REE patterns of the groundwaters are compared to those of modern seawater (open ocean and nearshore), Holocene reefal microbial carbonates and corals, and Archean chemical sediments using statistical means (i.e., ANOVA and Wilcoxon analyses) in order to quantify the similarities and/or differences in the REE patterns. Shale-normalized (SN) Ce anomalies and measures of REE fractionation [i.e., (La/Yb)_SN, (Pr/Yb)_SN, (Nd/Yb)_SN, and (Gd/Yb)_SN] of the central México groundwater samples are statistically indistinguishable from those of modern seawater. Moreover, except for differences in the Ce anomalies, which are lacking in Archean chemical sediments, the REE patterns of the central México groundwaters are also statistically similar to REE patterns of Archean chemical sediments, especially those of the 3.45 Ga Strelley Pool Chert. Consequently, we suggest that without additional information, it may be premature to unequivocally conclude that Archean chemical sediments record REE signatures of an Archean ocean.     

Neodymium isotopes in seawater from the Barents Sea and Fram Strait Arctic-Atlantic gateways

The neodymium concentration, C_Nd, and isotopic composition, ε_Nd, in seawater have been determined in the water column at five sites in the Barents Sea-Fram Strait area where most of the water exchange between the Arctic Ocean and the North Atlantic takes place. In the main Arctic Ocean inflow branch across the Barents Sea the concentration and isotopic composition (C_Nd = 15.5 pmol/kg and ε_Nd = −10.8) are similar to those reported for the northeastern Nordic Seas, which is consistent with this region being a source area for the Arctic inflow. Due to the addition of Nd from Svalbard shelf sediments, the C_Nd in the surface waters above 150 m, in the Fram Strait inflow branch is higher by a factor of 2 and the ε_Nd is shifted to lower values (−11.8).In the stratified Nansen Basin, where cold low salinity water overlies warmer Atlantic water the C_Nd and ε_Nd do not vary with the vertical temperature-salinity structure but are essentially constant and similar to those of the Atlantic inflow throughout the entire water column, down to 3700 m depth, which indicates that the Nd is to a large extent of Atlantic origin.Compared to the Atlantic inflow water, the Nd in the major Arctic Ocean outflow, the Fram Strait, show higher C_Nd in the surface waters above 150 m, and a higher ε_Nd (−9.8) throughout the entire water column down to 1300 m depth. Sources for the more radiogenic Nd isotopic composition in deep water of the Fram Strait outflow most likely involve boundary exchange with sediments on the shelf and slope as the water passes along the Canadian archipelago. River water is a possible source in the surface water but it also seems likely that Pacific water Nd, modified by interactions on the shelf, is an important component in the Fram Strait surface outflow. Changes in the relative proportions of inflow of river water and flow of Pacific water through the Arctic Ocean could thus influence the isotopic composition of Nd in the North Atlantic.     

Nd isotopic composition in the central North Pacific

Three vertical profiles of seawater concentration and isotopic composition of Nd were determined for the western to central North Pacific Ocean.In the subarctic oceanic region, at depths greater than 500 m, one vertical profile of Nd isotopic composition was indistinguishable from most previously reported profiles from here. The data indicate a rather homogeneous Nd isotopic composition in the subarctic oceanic region at middle to deep depths (>500 m). Two stations in the subtropical oceanic region exhibited similar Nd isotopic composition profiles to those previously reported. The maxima ε_Nd values at depths of 800-1000 m (ε_Nd = −3.4 to −2.7), which correspond to the North Pacific Intermediate Water (NPIW), are found at both subtropical stations. This implies a ubiquitous distribution of NPIW showing a radiogenic ε_Nd value in the North Pacific. The subsurface minimum at a depth of ∼200 m, which indicates the penetration of the North Pacific Tropical Water (NPTW) with an unradiogenic Nd isotopic signal, was observed at one station in the western Pacific. This station had much lower ε_Nd than the central station at depths around 5000 m, suggesting the greater prominence of Antarctic Bottom Water (AABW) in the western subtropical Pacific than in the central to eastern subtropical Pacific.Results of a model calculation assuming boundary exchange indicate that the Hawaiian Islands play an important role in supplying radiogenic Nd to the central Pacific, similar to some continental margins.We show that Nd isotopic composition is a versatile tracer for ocean circulation and the geochemical cycle of Nd in the North Pacific. Further studies on the distribution of Nd isotopic composition in the Pacific Ocean, including the Southern Pacific, will better elucidate the circulation and geochemical cycle of Nd in the Pacific.     

Paleo- and Mesoarchean TTG-sanukitoid to high-K granite cycles in the southern São Francisco craton,SE Brazil

The generation of the continental crust is widely accepted to have taken place predominantly in the Archean, when TTG magmatism associated with greenstone-belt supracrustal succession development was typically followed by emplacement of high-K granites before crustal stabilization. This study focuses on the Campos Gerais complex (CGC), which is an Archean granite-greenstone belt lithological association in a tectonic window located in the southwesternmost portion of the São Francisco craton (SFC). The CGC is an important segment of Paleo- to Mesoarchean continental crust to be integrated into paleogeographic reconstructions prior to the transition into the Paleoproterozoic. This investigation reports field relationships, 28 major and trace element compositions, U–Pb (zircon) geochronological results, and Hf and Sm–Nd isotope data for orthogneiss and amphibolite samples. The results indicate that the CGC records a complex Archean crustal evolution, where voluminous 2.97 Ga TTG tonalites and trondhjemites (ε_Nd(t) =  ? 4.7; T_DM = 3.24 Ga) were followed by 2.89 Ga sanukitoid tonalite production (ε_Nd(t) =  ? 1.9; T_DM = 3.02 Ga), broadly coeval with the development of the Fortaleza de Minas and Pitangui greenstone-belts. These events are interpreted to represent the initial stage of an important subduction-accretion tectonic cycle, which ended with the emplacement of 2.82–2.81 Ga high-K leucogranites and migmatization of the TTG-sanukitoid crust, with hybrid and two-mica, peraluminous compositions (ε_Nd(t) =  ? 8.0 to ? 8.6; T_DM = 3.57 – 3.34 Ga). The presence of inherited zircons with ²⁰⁷Pb/²⁰⁶Pb ages of 3.08 Ga, 3.29 Ga, 3.55 Ga and 3.62 Ga indicates that the Mesoarchean tectonic processes involved reworking of Meso- to Eo-archean crust. Renewed TTG magmatism took place at ca. 2.77 Ga represented by juvenile tonalite stocks (ε_Nd(t) = +1.0 to ? 1.5; T_DM = 2.80 – 2.88 Ga) which intrude the TTG-greenstone belt association. Crustal stabilization was attained by 2.67 Ga, allowing for the emplacement of within-plate tholeiitic amphibolites (ε_Nd(t) =  ? 3.1; T_DM = 2.87 Ga). The CGC shows important tectonic diachronism with respect to other Archean terrains in the southern São Francisco craton, including an independent Meso- to Neoarchean crustal evolution.     

The distribution of neodymium isotopes in Arctic Ocean basins

Nd concentration and isotope data have been obtained for the Canada, Amundsen, and Makarov Basins of the Arctic Ocean. A pattern of high Nd concentrations (up to 58 pM) at shallow depths is seen throughout the Arctic, and is distinct from that generally seen in other oceans where surface waters are relatively depleted. A range of isotopic variations across the Arctic and within individual depth profiles reflects the different sources of waters. The dominant source of water, and so Nd, is the Atlantic Ocean, with lesser contributions from the Pacific and Arctic Rivers. Radiogenic isotope Nd signatures (up to ε_Nd = −6.5) can be traced in Pacific water flowing into the Canada Basin. Waters from rivers draining older terrains provide very unradiogenic Nd (down to ε_Nd = −14.2) that can be traced in surface waters across much of the Eurasian Basin. A distinct feature of the Arctic is the general influence of the shelves on the Nd concentrations of waters flowing into the basins, either from the Pacific across the Chukchi Sea, or from across the extensive Siberian shelves. Water-shelf interaction results in an increase in Nd concentration without significant changes in salinity in essentially all waters in the Arctic, through processes that are not yet well understood. In estuarine regions other processes modify the Nd signal of freshwater components supplied into the Arctic Basin, and possibly also contribute to sedimentary Nd that may be subsequently involved in sediment-water interactions. Mixing relationships indicate that in estuaries, Nd is removed from major river waters to different degrees. Deep waters in the Arctic are higher in Nd than the inflowing Atlantic waters, apparently through enrichments of waters on the shelves that are involved in ventilating the deep basins. These enrichments generally have not resulted in major shifts in the isotopic compositions of the deep waters in the Makarov Basin (ε_Nd ∼ −10.5), but have created distinctive Nd isotope signatures that were found near the margin of the Canada Basin (with ε_Nd ∼ −9.0). The deep waters of the Amundsen Basin are also distinct from the Atlantic waters (with ε_Nd = −12.3), indicating that there has been limited inflow from the adjacent Makarov Basin through the Lomonosov Ridge.     

Re-Os and Mo isotope systematics of black shales from the Middle Proterozoic Velkerri and Wollogorang Formations, McArthur Basin, northern Australia

Joint application of the Mo isotope paleoredox proxy and Re-Os deposition-age geochronometer to euxinic black shales has potential for tracing the evolution of ocean redox chemistry over geological time. Here, we report new Re-Os and Mo isotope data for the Mesoproterozoic Velkerri Formation (Roper Group) and Paleoproterozoic Wollogorang Formation (Tawallah Group), McArthur Basin, northern Australia. New Re-Os ages of 1361 ± 21 Ma (2σ, n = 14, mean square of weighted deviates [MSWD] = 1.3, Model 1) and 1417 ± 29 Ma (2σ, n = 12, MSWD = 1.3, Model 1) constrain the depositional age of the Velkerri Formation and its contained biomarkers, as well as acritarchs and microfossils from the Roper Group. Black shales from the upper Velkerri Formation have high Mo abundances (105-119 ppm) and degree of pyritization [DOP] values (0.90-0.92) implying quantitative conversion of molybdate (MoO₄²⁻) to thiomolybdate (MoS₄²⁻) in overlying bottom waters. The average δ^97/95Mo (0.72 ± 0.10‰, 2σ, n = 6) of these shales is consistent with previous data, but represents a significantly more precise determination for global seawater δ^97/95Mo at 1.4 Ga. This value is lighter than present-day seawater by ∼0.85‰ and reflects expanded strongly euxinic deep ocean conditions ([H₂S]_aq > 11 μM) relative to oxic, suboxic, and weakly/intermittently euxinic ([H₂S]_aq < 11 μM) marine deposition in the 1.4 Ga oceans. Mass-balance modelling suggests Mo removal into strongly euxinic and oxic sediments may have comprised 30-70% and less than 15%, respectively, of the oceanic Mo sink at 1.4 Ga as opposed to 5% and 35% today, respectively.The Re-Os radioisotope system in organic-rich shales serves as a test for post-depositional alteration that could affect the usefulness of paleoredox tracers such as Mo stable isotopes. Re-Os isotope data for the Wollogorang Formation black shales are scattered and yield a highly imprecise date of 1359 ± 150 Ma (2σ, n = 21, MSWD = 85, Model 3). This age is younger than U-Pb zircon ages from interbedded tuffs that constrain the age of deposition at ca. 1730 Ma. In conjunction with previous petrological, geochemical, and paleomagnetic data, the Re-Os isotope data suggest hydrothermal fluid flow through the Wollogorang Formation, possibly associated with formation of the ca. 1640 Ma McArthur River Pb-Zn-Ag sedimentary exhalative deposit, resulted in post-depositional mobilization of Re and Os. Based on the degree of deviation of the Re-Os data from a 1730 Ma reference line, open-system behavior of Re and Os was greatest near the base of the black shale unit. Wollogorang Formation black shales are enriched in Mo (41-58 ppm), but are characterized by variable δ^97/95Mo (0.3-0.8‰) and DOP (0.57-0.92). The lightest δ^97/95Mo values occur near the base of the black shale unit. Based on the Re-Os systematics, hydrothermal fluids have probably overprinted the authigenic δ^97/95Mo signature in those shales. However, the heaviest δ^97/95Mo values in the Wollogorang Formation come from stratigraphically higher shales, and are similar to those observed for the Velkerri Formation, and thus may reflect seawater δ^97/95Mo at 1.73 Ga.     

High-pressure metamorphic rocks in the Borborema Province,Northeast Brazil: Reworking of Archean oceanic crust during proterozoic orogenies

We present the first evidence of Archean oceanic crust submitted to Proterozoic high-pressure (HP) metamorphism in the South American Platform. Sm–Nd and Lu–Hf isotopic data combined with U–Pb geochronological data from the Campo Grande area, Rio Grande do Norte domain, in the Northern Borborema Province, reflect a complex Archean (2.9 ​Ga and 2.6 ​Ga) and Paleoproterozoic (2.0 ​Ga) evolution, culminating in the Neoproterozoic Brasiliano/Pan-African orogeny (ca. 600 Ma). The preserved mafic rocks contain massive poikiloblastic garnet and granoblastic amphibole with variable proportions of plagioclase ​+ ​diopside in symplectitic texture, typical of high-pressure rocks. These clinopyroxene-garnet amphibolites and the more common garnet amphibolites from the Campo Grande area are exposed as rare lenses within an Archean migmatite complex. The amphibolite lenses represent 2.65 ​Ga juvenile tholeiitic magmatism derived from depleted mantle sources (positive ε_Hf(t) values of +3.81 to +30.66) later enriched by mantle metasomatism (negative ε_Nd(t) values of –7.97). Chondrite and Primitive Mantle-normalized REE of analyzed samples and discriminant diagrams define two different oceanic affinities, with E-MORB and OIB signature. Negative Eu anomalies (Eu/Eu1 ​= ​0.75–0.95) indicate depletion of plagioclase in the source. Inherited zircon cores of 3.0–2.9 ​Ga in analyzed samples indicate that the Neoarchean tholeiitic magmatism was emplaced into 2923 ​± ​14 ​Ma old Mesoarchean crust (ε_Nd(t) ​= ​–2.58 and Nd T_DM ​= ​3.2 ​Ga) of the Rio Grande do Norte domain. The age of retro-eclogite facies metamorphism is not yet completely understood. We suggest that two high-grade metamorphic events are recognized in the mafic rocks: the first at 2.0 ​Ga, recorded in some samples, and the second, at ca. 600 Ma, stronger and more pervasive and recorded in several of the mafic rock samples. The Neoproterozoic zircon grains are found in symplectite texture as inclusions in the garnet grains and represent the age of HP conditions in the area. These zircon grains show a younger cluster of concordant analyses between 623 ​± ​3 ​Ma and 592 ​± ​5 ​Ma with ε_Hf(t) values of +0.74 to –65.88. Thus, the Campo Grande rock assemblage is composed of Archean units that were amalgamated to West Gondwana during Neoproterozoic Brasiliano orogeny continent-continent collision and crustal reworking.     

Neodymium isotopes in the Mediterranean Sea: comparison between seawater and sediment signals

Nine depth-profiles of dissolved Nd concentrations and isotopic ratios (ε_Nd) were obtained in the Levantine Basin, the Ionian, the Aegean, the Alboran Seas and the Strait of Gibraltar. Thirteen core-top sediments and Nile River particle samples were also analyzed (leached with 1 N HCl, acetic acid or hydroxylamine hydrochloride). The seawater ε_Nd values become more radiogenic during the eastward circulation in the Mediterranean Sea. The relationship between salinity and the seawater ε_Nd shows that the Nd isotopic signature is more conservative than salinity in the Mediterranean Sea. The water mass with the highest ε_Nd (−4.8) is found at about 200 m in the easternmost Levantine basin. The average ε_Nd value for deep waters is −7.0 in the eastern basin, 2.5 ε-units higher than in the western basin. By examining the sensitivity of seawater ε_Nd to Nd inputs from the Nile, we conclude that the most significant radiogenic Nd source is partially dissolved Nile River particles. The Nd flux from the Nile River water has a minor influence on the Mediterranean seawater ε_Nd. Except for the easternmost Levantine Basin, the leachate ε_Nd values are consistent with the seawater values. In the easternmost Levantine Basin, the leachate ε_Nd values obtained with HCl leaching are systematically higher than the seawater values. The relationship between leachate and residual ε_Nd values indicates that the HCl leaching partially dissolves lithogenic Nd, so the dissolution of Nile River particles is the cause of the observed shift. Some ε_Nd values obtained with hydroxylamine hydrochloride leaching are higher than those obtained with HCl leaching. Although the reason for this shift is not clear, ⁸⁷Sr/⁸⁶Sr successfully detects the presence of a nonmarine component in the leachate. Our results suggest that leaching performance may vary with the mineralogy of marine sediments, at least in the case of the Mediterranean Sea.     

Melting of enriched Archean subcontinental lithospheric mantle: Evidence from the ca. 1760 Ma volcanic rocks of the Xiong’er Group,southern margin of the North China Craton

The Xiong’er Group is an important geologic unit in the southern margin of the North China Craton. It is dominated by the volcanic rocks, dated at 1763 ± 15 Ma, that have SiO₂ contents ranging from 52.10 wt% to 73.51 wt%. These volcanic rocks are sub-alkaline and can be classified into three subgroups: basaltic andesites, andesites and rhyolites. They unexceptionally show enrichment of light rare earth elements (LREE) and share similar trace element patterns. Depletions in Nb, Ta, Sr, P and Ti relative to the adjacent elements are evident for all the samples. The volcanic rocks are evolved with low MgO contents (0.29–5.88 wt%) and accordingly low Mg^# values of 11–53. The Nd isotopes are enriched and show a weak variation with ?_Nd(t) = −7.12 to −9.63. Zircon Hf isotopes are also enriched with ?_Hf(t) = −12.02 ± 0.45. The volcanic rocks of the Xiong’er Group are interpreted to represent fractional crystallization of a common mantle source. The volcanic rocks might have been generated by high-degree partial melting of a lithospheric mantle that was originally modified by the oceanic subduction in the Late Archean. This brings a correlation with the subduction-modified lithospheric mantle in an extensional setting during breakup of the Columbia supercontinent in the late Paleoproterozoic, rather than in an arc setting. The elevated SiO₂ contents and evolved radiogenic isotope features indicate the possible incorporation into their source of lower crustal materials that have similar Nd isotopic characteristics to the subcontinental lithospheric mantle. The existence of extensive Xiong’er volcanic rocks (60,000 km²) indicates an early large-scale subduction-related metasomatism in the area and probably suggest a flat subduction model for the plate-margin magmatism in the Late Archean.     

http://www.sciencedirect.com/science/article/pii/S1674987113000820

The combined use of Hf,Nd and Sr isotopes is more useful in understanding the supercontinent cycle than the use of only Hf isotopic data from detrital zircons.Sr and Nd seawater isotopes,although not as precise as εNd and εHf distributions,also record input from ocean ridge systems.Unlike detrital zircons where sources cannot be precisely located because of crustal recycling,both the location and tectonic setting often can be constrained for whole-rock Nd isotopic data.Furthermore,primary zircon sources may not reside on the same continent as derivative detrital zircons due to supercontinent breakup and assembly.Common to all of the isotopic studies are geographic sampling biases reflecting outcrop distributions,river system sampling,or geologists,and these may be responsible for most of the decorrelation observed between isotopic systems.Distributions between 3.5 and 2 Ga based on εHf median values of four detrital zircon databases as well as our compiled εNd database are noisy but uniformly distributed in time,whereas data between 2 and 1 Ga data are more tightly clustered with smaller variations.Grouped age peaks suggest that both isotopic systems are sampling similar types of orogens.Only after 1 Ga and before 3.5 Ga do we see wide variations and significant disagreement between databases,which may partially reflect variations in both the number of sample locations and the number of samples per location.External and internal orogens show similar patterns in εNd and εHfwith age suggesting that both juvenile and reworked crustal components are produced in both types of orogens with similar proportions.However,both types of orogens clearly produce more juvenile isotopic signatures in retreating mode than in advancing mode.Many secular changes in εHf and εNd distributions correlate with the supercontinent cycle.Although supercontinent breakup is correlated with short-lived decreasing εHf and εNd （≤ 100 Myr） for most supercontinents,there is no isotopic evidence for the breakup of the Paleoproterozoic supercontinent Nuna.Assembly of supercontinents by extroversion is recorded by decreasing εNd in granitoids and metasediments and decreasing εHf in zircons,attesting to the role of crustal reworking in external orogens in advancing mode.As expected,seawater Sr isotopes increase and seawater Nd isotopes decrease during supercontinent assembly by extroversion.Pangea is the only supercontinent that has a clear isotopic record of introversion assembly,during which median εNd and εHf rise rapidly for ≤ 100 Myr.Although expected to increase,radiogenic seawater Sr decreases （and seawater Nd increases） during assembly of Pangea,a feature that may be caused by juvenile input into the oceans from new ocean ridges and external orogens in retreating mode.The fact that a probable onset of plate tectonics around 3 Ga is not recorded in isotopic distributions may be due the existence of widespread felsic crust formed prior to the onset of plate tectonics in a stagnant lid tectonic regime,as supported by Nd and Hf model ages.     

Isotope geochemistry and geochronology of the Nico Pérez Terrane,Rio de la Plata Craton,Uruguay

U–Pb SHRIMP zircon geochronology, bulk-rock geochemistry, and Sr–Nd isotopic data are herein presented in order to better constrain the tectonic evolution of the Nico Pérez Terrane (NPT), Uruguay. The studies are focused on two key geological units located in the southern part of the NPT, namely Carapé Complex (CC) and Lavalleja Metamorphic Complex (LMC). The Carapé Complex, previously interpreted as part of a remnant magmatic arc, formed at 1.75 Ga mainly by partial melting of Archean crust (T_DM model ages between 2.8 and 3.0 Ga with strong negative ɛ_Nd (t) values). The Lavalleja Metamorphic Complex, previously interpreted as a back-arc basin, has volcanic units formed at 0.59 Ga during the Brasiliano Cycle, but may also contain older (Paleoproterozoic) units. The geochemistry of the LMC meta-igneous rocks indicates a complex scenario. Two distinct signatures have been recognized, one similar to MORBs and the other similar OIBs. Sm–Nd T_DM model ages of basic rocks present a bimodal (Paleoproterozoic and Archean) distribution, which is also recognized in several other units of the NPT. In the light of new results, we conclude that the NPT represents a cratonic margin setting, characterized by the stacking of lithotectonic assemblages with Archean, Paleoproterozoic, and Neoproterozoic age at the margin of the Rio de la Plata Craton.     

Provenance ages and alteration histories of shales from the Middle Archean Buhwa greenstone belt, Zimbabwe: Nd and Pb isotopic evidence

Shales of the ca. 3.0 Ga Buhwa Greenstone Belt, Zimbabwe, were derived from a compositionally diverse provenance whose ages, determined by ion probe analyses of detrital zircons in interbedded sandstones, range from 3.8 to 3.1 Ga. Geochemical data for the shales were previously interpreted to indicate that sediments had been derived from an intensely weathered source. REE concentrations in the shales were interpreted to suggest that the provenance was compositionally mixed, with components of felsic (tonalite and alkalic granitoid) and mafic rocks. Sm/Nd and Nd isotopic compositions of these rocks can be used to model initial Nd isotopic ratios at the time of sedimentation (ε_Ndsed), as well as model crustal formation ages (T_DM). The former, at the age of sedimentation, range from +0.6 to −10.8, consistent with a range of provenance ages. The latter range from 4.46 Ga to 2.99 Ga. The oldest crustal formation ages, up to 0.7 Ga older than known detrital components, are interpreted here to indicate that the Sm-Nd system of the sediments experienced open system behavior. The implied alteration would have included an increase in Sm/Nd by about 20-25 percent, probably in the form of preferential loss of Nd with respect to Sm. The Pb isotopic compositions of whole rock samples are quite radiogenic, with a range of ²⁰⁶Pb/²⁰⁴Pb from 25.5 to 154. An array of ten samples lies scattered about a line with a ²⁰⁷Pb/²⁰⁴Pb -²⁰⁶Pb/²⁰⁴Pb slope age of about 2.73 Ga. Five individual samples were sequentially leached to further test the timing and characteristics of this U-Th-Pb alteration event. These arrays of a whole rock, three leach steps, and a residue also form linear Pb-Pb arrays (one is more scattered) with ages ranging from 2260 ± 360 Ma to 2824 ± 170 Ma, suggesting that all samples experienced a latest Archean to earliest Proterozoic enrichment in U/Pb. This age range also may be the approximate age of Sm/Nd enrichment for the shales. All samples, both whole rocks and leached samples, lie grouped on a ²⁰⁸Pb/²⁰⁴Pb - ²⁰⁶Pb/²⁰⁴Pb diagram around a line with ²³²Th/²³⁸U = 3.5 (2.9 to 3.9). Because of the lack of large differences in the Th/U of the samples through large ranges of U/Pb, we interpret this consistency in Th/U to mean that the shales of the Buhwa belt experienced Pb loss, rather than U and Th gain. Circumstances that may be responsible for Pb loss in a sedimentary basin include loss of saline fluids during basin dewatering. Such an event would likely have been related to folding associated with the thrusting and magmatic intrusion of the adjacent Limpopo Belt, suggesting that uplift, dewatering, and geochemical and isotopic alteration can be genetically related.     

Nd isotopic constraints on crustal formation in the North China Craton

Recent tectonic analysis suggests that the North China Craton consists of two Archean continental blocks, called the Eastern and Western Blocks, separated by the Paleoproterozoic Trans-North China Orogen. Although the published geochronological data are not sufficient to constrain the detailed tectonothermal evolution of the craton, the available Nd isotopic data show some important differences in Nd model ages between the tectonic units. The Eastern Block shows two main Nd model age peaks, one between 3.6 and 3.2 Ga and the other between 3.0 and 2.6 Ga. Limited Nd isotopic data from the Western Block show a large range of model ages between 3.2 and 2.4 Ga. These differences are consistent with the recently-proposed model.The Nd isotopic data from mantle-derived mafic rocks indicate that the mantle beneath the North China Craton was depleted in the Archean, consistent with major crustal growth during this period. In the Paleoproterozoic, however, the mantle-derived mafic rocks show negative ε_Nd(t) values, implying crustal contamination. This may have resulted from subduction and collision between the Eastern and Western Block, implying that the mechanisms of crustal formation and evolution may have been different between the Archean and Paleoproterozoic.The North China Craton was re-activated by addition of mantle-derived magma into the lower crust in the late Mesozoic, resulting in rejuvenation of the lower crust. This indicates that underplating is also an important mechanism for continental addition, although in this case it may not equate to crustal growth, since it was preceded by removal of lithospheric mantle and possible some lower crust.     

Permian volcanic rocks from the Apuseni Mountains (Romania): Geochemistry and tectonic constraints

An Early Permian volcanic assemblage is well exposed in the central-western part of the Apuseni Mountains (Romania). The rocks are represented by rhyolites, basalts and subordinate andesites suggesting a bimodal volcanic activity that is intimately associated with a post-orogenic (Variscan) syn-sedimentary intra-basinal continental molasse sequences. The mafic and mafic-intermediate rocks belong to sub-alkaline tholeiitic series were separated in three groups (I–III) showing a high Th and Pb abundances, depletion in Nb, Ta and Sr, and slightly enriched in LREE patterns (La_N/Yb_N = 1.4–4.4). Isotopically, the rocks of Group I have the initial ratios ⁸⁷Sr/⁸⁶Sr_(i) = 0.709351–0.707112, ¹⁴³Nd/¹⁴⁴Nd_(i) = 0.512490–0.512588 and high positive ?_Nd270 values from 3.9 to 5.80; the rocks of Group II present for the initial ratios values ⁸⁷Sr/⁸⁶Sr_(i) = 0.709434–0.710092, ¹⁴³Nd/¹⁴⁴Nd_(i) = 0.512231–0.512210 and for ?_Nd270 the negative values from −1.17 to −1.56; the rocks of Group III display for the initial ratios the values ⁸⁷Sr/⁸⁶Sr_(i) = 0.710751–0.709448, ¹⁴³Nd/¹⁴⁴Nd_(i) = 0.512347–0.512411 and for ?_Nd270 the positive values from 1.64 to 2.35. The rocks resembling continental tholeiites, suggest a mantle origin and were further affected by fractionation and crustal contamination. In addition, the REE geochemistry (1 > Sm_N/Yb_N < 2.5; 0.9 > La_N/Sm_N < 2.5) suggests that these rocks were generated by high percentage partial melting of a metasomatized mantle in the garnet peridotite facies. The felsic rocks are enriched in Cs, Rb Th and U and depleted in Nb, Ta, Sr, Eu, and Ti. The REE fractionation patterns show a strong negative Eu anomaly (Eu/Eu* = 0.23–0.40). The felsic rocks show the initial ratios the values: ⁸⁷Sr/⁸⁶Sr_(i) = 0.704096–0.707805, ¹⁴³Nd/¹⁴⁴Nd_(i) = 0.512012–0.512021 and for ?_Nd270 the negative values from −5.27 to −5.44. They suggest to be generated within the lower crust during the emplacement of mantle-derived magmas that provided necessary heat to crustal partial melting.     

Evolution of the depleted mantle: Hf isotope evidence from juvenile rocks through time

The covariant behavior of Lu-Hf and Sm-Nd isotopes during most magmatic processes has long been recognized, but the details of this behavior in the depleted mantle reservoir have not been adequately examined. We report new whole-rock Hf and Nd isotope data for 1) juvenile, mantle-derived rocks, mid-Archean to Mesozoic in age, and 2) early Archean gneisses from West Greenland. Hf and Nd isotopic compositions of the juvenile rocks are well correlated, with the best fit corresponding to the equation ε_Hf = 1.40 ε_Nd + 2.1, and is similar to the collective Hf-Nd correlation for terrestrial samples of ε_Hf = 1.36 ε_Nd + 3.0. The early Archean Greenland gneisses, in contrast, have an extreme range in ε_Nd values (⁻4.4 to ⁺4.2; Bennett et al., 1993) that is not mirrored by the Hf isotopic system. The ε_Hf values for these rocks are consistently positive and have much less variation (0 to ⁺3.4) than their ε_Nd counterparts.The information from the Hf isotopic compositions of the West Greenland gneisses portrays an early Archean mantle that is relatively isotopically homogeneous at 3.8 to 3.6 Ga and moderately depleted in incompatible elements. There is no evidence that any of these gneisses have been derived from an enriched reservoir. The Hf isotopic data are in stark contrast to the Nd isotopic record and strongly imply that the picture of extreme initial isotopic heterogeneity indicated by Nd isotopes is not a real feature of the West Greenland gneisses but is rather an artifact produced by disturbances in the Sm-Nd isotope system of these rocks.Although Hf and Nd isotopic data do not uniquely constrain either the nature of the earliest crust or the timing of crustal growth, the most probable candidate for the enriched reservoir complementary to the depleted mantle in the pre-4.0 Ga Earth is a mafic, oceanic-type crust. In order to explain the predominantly positive ε_Hf and ε_Nd values for the early Archean rocks, this crust must have had a short residence time at the surface of the Earth before returning to the mantle where it was isolated from mixing with the depleted mantle for several hundred million years. The following period from 3.5 to 2.7 Ga may mark a transition during which this early formed mafic crust was mixed progressively back into the depleted mantle reservoir. While a present-day volume of continental crust at 4.0 Ga cannot be excluded on isotopic grounds, we find such a scenario unlikely based on the lack of direct isotopic and physical evidence for its existence. An important aspect of crustal growth and evolution, therefore, may be the transformation of the enriched reservoir from being predominantly mafic in the early Earth to becoming progressively more sialic through time.     

Nd isotopic composition of Late Devonian seawater in western Thailand: Geotectonic implications for the origin of the Sibumasu terrane

Conodonts collected from sections near the small towns of Thong Pha Phum and Mae Sariang in the westernmost part of Thailand are used to reconstruct the neodymium (Nd) isotopic composition of seawater during the Late Devonian. The study provides the first Devonian seawater signatures recognized within the Australian shelf of northeastern Gondwana and the adjacent Paleotethys Ocean. At Thong Pha Phum site, the seawater was characterized by very low ε_Nd values (from − 13.1 to − 18.2) and very high Sm/Nd ratios (between 0.36 and 0.66). In contrast, the seawater at the Mae Sariang site was characterized by much more radiogenic signatures (ε_Nd values from − 8.7 to − 11.1) and uniform, low Sm/Nd ratios (between 0.20 and 0.23). Extremely low ε_Nd values recognized at Thong Pha Phum attest to a passive margin continental setting and a paleogeographic position very close to a continental area where Paleoproterozoic and Neoarchean rocks were eroded. Thus, the isotopic data provide strong evidence that during Late Devonian time the Sibumasu terrane was situated in the proximity to the Archean cratons of Western Australia, presumably adjacent to the Carnarvon intracratonic basin. Moreover, Sibumasu may not have been situated in an outboard position on the shelf, as previously suggested, but could have been directly attached to the Australian continental crust. By contrast, low and uniform Sm/Nd ratios of seawater at Mae Sariang resemble those of the Variscan and the present-day oceanic seawaters. Therefore, a pelagic setting within the Paleotethys Ocean is postulated for the Mae Sariang succession. This conclusion is also constrained by minor temporal changes in ε_Nd values and suggests that the Paleozoic of Mae Sariang is not part of the Sibumasu terrane but belongs to the Inthanon Zone.     

Tracing Nile sediment sources by Sr and Nd isotope signatures (Uganda, Ethiopia, Sudan)

Strontium and neodymium isotopes, measured on diverse mud and sand fractions of sediment in transit along all major Nile branches, identify detritus sourced from Precambrian basements, Mesozoic strata, and Tertiary volcanic rocks exposed along the shoulders of the East African rift and in Ethiopian highlands. Sr and Nd isotopic ratios reflect the weighted average of detrital components generated in different catchments, allowing us to discriminate provenance, calculate sediment budgets, and investigate grain-size and hydraulic-sorting effects.⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd range, respectively, from as high as 0.722 and as low as 0.5108 for sediment derived from Archean gneisses in northern Uganda, to 0.705 and 0.5127 for sediment derived from Neoproterozoic Ethiopian and Eritrean basements. ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd, ranging 0.705-0.709 and 0.5124-0.5130 for Blue Nile tributaries, are 0.704-0.705 and 0.5127-0.5128 for largely volcaniclastic sediments of River Tekeze-Atbara, and 0.705-0.706 and 0.5126-0.5127 for main Nile sediments upstream Lake Nasser.Model mantle derivation ages (t_DM), oldest in Uganda where sediment is principally derived from the Congo Craton (3.4-3.0 Ga for Victoria and Albert Nile), progressively decrease northward across the Saharan Metacraton, from 2.6 Ga (Bahr el Jebel in South Sudan), to 2.4-2.2 Ga (Bahr ez Zeraf across the Sudd), and finally 1.6-1.3 Ga (White Nile upstream Khartoum). Instead, t_DM ages of Sobat mud increase from 0.9 to 1.5 Ga across the Machar marshes. T_DM ages are younger for sediments shed by Ethiopian (1.2-0.7 Ga) and Eritrean basements (1.5-1.2 Ga), and youngest for sediments shed from Ethiopian flood basalts (0.3-0.2 Ga).Integrated geochemical, mineralogical, and settling-equivalence analyses suggest influence on the Nd isotopic signal by volcanic lithic grains and titanite rather than by LREE-rich monazite or allanite. Because contributions by ultradense minerals is subordinate, intrasample variability of Sr and Nd ratios is minor. In Blue Nile, Atbara and main Nile sediments of mixed provenance, however, the Nd ratio tends to be higher and t_DM ages lower in largely volcaniclastic mud than in mixed volcaniclastic/metamorphiclastic sand.The complete geochemical database presented here, coupled with high-resolution bulk-petrography and heavy-mineral data, provides a key to reconstructing erosion patterns and detrital fluxes across the whole Nile basin, and to investigate and understand how sources of sediment have changed in the historical and pre-historical past in relation to shifting climatic zones across arid northern Africa.