Hafnium isotopes in Arctic Ocean water

The first isotopic compositions of dissolved hafnium in seawater from across the Arctic Ocean are reported. Most samples from the four sub-basins of the Arctic Ocean have values within error of an average of ε_Hf = +0.8. Combined Hf-Nd isotope compositions do not fall on the well-established positive correlation for mantle and crustal rocks. Instead, Arctic waters have Hf that is more radiogenic than that typically found in rocks with similar Nd isotope compositions, a feature previously found in ferromanganese crusts and waters from the Pacific Ocean. Arctic seawater samples generally fall on the lower part of the ferromanganese crust array, reflecting influences of inputs from Arctic rivers and interactions of shelf waters with underlying sediments. Arctic rivers have much higher Hf concentrations (7-30 pM) than Arctic seawater (0.36-4.2 pM). Water from the Mackenzie River has the least radiogenic Hf, with ε_Hf = −7.1 ± 1.7, and plots furthest away from the ferromanganese crust array, while waters from the Ob, Yenisey, and Lena Rivers have values that are indistinguishable from most Arctic waters. In the Amundsen, Makarov, and Canada basins, Hf concentrations are highest at the surface and lowest in the deeper waters, reflecting the influences of riverine inputs and of waters that have flowed over the extensive Siberian continental shelves and have Nd and Hf characteristics that reflect water-sediment interactions. This is in contrast to the relatively low near surface Hf concentrations reported for locations elsewhere. The Pacific water layer in the Canada Basin exhibits the highest value of ε_Hf = +6.8 ± 1.8, reflecting the Hf isotopic composition of waters entering the Arctic from the Pacific Ocean. Mixing relationships indicate that a substantial fraction of the Hf in the Mackenzie River is lost during estuarine mixing; the behaviour of Hf from other rivers is less constrained.     

Hafnium and neodymium isotopes in surface waters of the eastern Atlantic Ocean: Implications for sources and inputs of trace metals to the ocean

We present hafnium (Hf) and neodymium (Nd) isotopic compositions and concentrations in surface waters of the eastern Atlantic Ocean between the coast of Spain and South-Africa. These data are complemented by Hf and Nd isotopic and concentration data, as well as rare earth element (REE) concentrations, in Saharan dust.Hafnium concentrations range between a maximum of 0.52 pmol/kg in the area of the Canary Islands and a minimum value of 0.08 pmol/kg in the southern Angola Basin. Neodymium concentrations also show a local maximum in the area of the Canary Islands (26 pmol/kg) but are even higher between ∼20°N and ∼4°N reaching maximum concentrations of 35 pmol/kg. These elevated concentrations provide evidence of inputs from weathering of the Canary Islands and from the partial dissolution of dust from the Sahara/Sahel region. The inputs from ocean island weathering are also reflected in radiogenic Hf and Nd isotopes.The Hf isotopic compositions of dust samples themselves are highly variable, ranging between ε_Hf = −20 and −0.6. The combined Hf and Nd isotopic compositions of dust plot close to the “terrestrial array” during periods of appreciable dust load in the atmosphere. During low atmospheric dust loading combined Hf and Nd isotopic compositions similar to seawater are observed. Most of the variability can be explained in terms of variable degrees of zircon loss from the dust samples, which in turn is linked to sorting during atmospheric transport to the eastern Atlantic Ocean and possibly presorting by sedimentary redistribution on the continent. In addition, increasing relative proportions of radiogenic clay minerals with decreasing grain size may contribute to the radiogenic Hf isotopic compositions observed.While the Nd isotopic composition in the surface ocean reflects the Nd isotopic composition of the Saharan dust adjacent to the Sahara/Sahel region, the release of Hf from that dust appears to be incongruent and results in surface ocean Hf isotopic compositions which are ∼10 ε_Hf more radiogenic than the bulk dust. Radiogenic Hf appears to be released from clays and possibly from trace apatite. Rare earth element patterns of dust samples indicate the presence of apatite but provide no evidence for ferromanganese grain coatings, suggesting that such coatings are insignificant in the release of Hf and Nd from Saharan dust to the surface ocean.The Nd isotopic composition of the surface waters becomes less radiogenic south of the equator, most likely reflecting the release of Nd from Congo river sediments. The release of Hf from Saharan dust and the Congo river sediments, however, does not produce distinct Hf isotopic signatures in the surface ocean, implying that the mobile fraction of Hf integrated over large continental areas is isotopically uniform. The Hf isotopic uniformity in the surface ocean means that the limited variability in deep water isotopic compositions is consistent with a short deep water residence time and reflects homogenous continental inputs rather than efficient deep water homogenization.     

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.     

The Hf-Nd isotopic composition of marine sediments

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

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.     

Precise determination of cadmium isotope fractionation in seawater by double spike MC-ICPMS

A new technique has been developed for the accurate and precise determination of the stable Cd isotope composition of seawater. The method utilizes a ¹¹⁰Cd-¹¹¹Cd double spike, and it involves separation of Cd from seawater by column chromatography and isotopic analyses by multiple collector inductively coupled plasma mass spectrometry. As a by-product, it also generates precise Cd concentration data. Repeated analyses of three pure Cd reference materials and three seawater samples yielded reproducibilities of about ±1.0 to ±1.6 ε^114/110Cd (2 SD), based on measurements that each consumed about ∼8 ng of natural Cd (ε^114/110Cd is the deviation of the ¹¹⁴Cd/¹¹⁰Cd isotope ratio of a sample from the standard in parts per 10,000). This demonstrates that the new double spike technique is superior to published methods of Cd isotope analyses, with regard to the acquisition of precise data for samples of limited size. Additional experiments showed that as little as 1-5 ng of seawater Cd could be analyzed with a precision of about ±2 to ±6 ε^114/110Cd (2 SD). The accuracy of the seawater isotope data was ascertained by experiments in which a Cd-free seawater matrix was doped with small quantities of isotopically well-characterized Cd. Repeated mass scans that were carried out on purified Cd fractions of several samples furthermore demonstrated the absence of significant spectral interferences. The isotope data that were acquired for the three seawater samples reveal, for the first time, small but resolvable Cd isotope fractionations in the marine environment. Cadmium-rich intermediate water from the North Pacific was found to have an isotope composition of ε^114/110Cd = 3.2 ± 1.0. In contrast, Cd-depleted seawater from the upper water column of the Atlantic and Arctic Oceans displayed isotope compositions of ε^114/110Cd = 6.4 ± 1.1 and 6.6 ± 1.6, respectively. These observations are in accord with the interpretation that the isotope effects are due to the biological fractionation that occurs during the uptake of dissolved seawater Cd by phytoplankton.     

Variations of Sr–Nd–Hf isotopic systematics in basalt during intensive weathering

The Sr–Nd–Hf isotopic compositions of both saprolites and parent rocks of a profile of intensively weathered Neogene basalt in Hainan, South China are reported in this paper to investigate changes of isotopic systematics with high masses. The results indicate that all these isotopic systematics show significant changes in saprolites compared to those in corresponding parent rocks. The ⁸⁷Sr/⁸⁶Sr system was more seriously affected by weathering processes than other isotope systems, with ε_Sr drifts 30 to 70 away from those of the parent rocks. In the upper profile (> 2.2 m), the Sr isotopes of the saprolites show an upward increasing trend with ε_Sr changing from ~ 50 at 2.2 m to ~ 70 at 0.5 m, accompanying a upward increasing of Sr concentrations, from ~ 10 μg/g to ~ 25 μg/g. As nearly all the Sr of the parent rock has been removed during intensive weathering in this profile, the upward increasing of Sr concentrations in the upper profile suggests import of extraneous Sr. Rainwater in this region, which enriches in Sr (up to 139 μg/L) from seawater, may be the important extraneous source. Thus, the Sr isotopes of the saprolites in the upper profile may be mainly influenced by import of extraneous materials, and the Sr isotopic characteristics may not be retained. In contrast, the ε_Nd and ε_Hf of the saprolites drift only 0–2.6 and 0–3.7 away from the parent rocks, respectively. The negative drifts of the ε_Nd and ε_Hf are coupled with Nd and Hf losses in the saprolites; i.e., larger proportions of Nd and Hf loss correspond to lower ε_Nd and ε_Hf. Compared with the relative high Nd and Hf concentrations of the saprolites, the contributions of extraneous Nd and Hf both from wet and dry deposits of aeolian input are negligible. Thus, the ε_Nd and ε_Hf changes in the profile are mainly resulted from consecutive removal of the Nd and Hf. Calculation indicates that the ¹⁴³Nd/¹⁴⁴Nd and ¹⁷⁶Hf/¹⁷⁷Hf ratios in saprolites are all significantly lower than their initial values in the parent rock. Simply removing part of the Nd and Hf by incongruent decomposing some of the minerals may not account for this. Fractionation should be happen, which ¹⁴³Nd and ¹⁷⁶Hf may be preferentially removed from the profile relative to ¹⁴⁴Nd and ¹⁷⁷Hf during intensive chemical weathering, resulting in lower ¹⁴³Nd/¹⁴⁴Nd and ¹⁷⁶Hf/¹⁷⁷Hf ratios in saprolites relative to the parent rock, even though details for this process is not known. A positive correlation is observed between the ε_Nd and ε_Hf of the saprolites. Interestingly, the saprolites with a net loss of Nd and Hf in the upper profile show good positive correlation, and the regression line parallels the terrestrial array. By contrast, saprolites with a net gain of Nd and Hf in the lower profile generally show higher ε_Hf values at a given ε_Nd value, and the regression line between these ε_Nd and ε_Hf appears to parallel the seawater array. This supports the hypothesis that the contribution of continental Hf from chemical weathering release is the key to the obliquity of the seawater array away from the terrestrial array of the global ε_Nd and ε_Hf correlation. Our results also indicate that caution is needed when using ε_Sr, ε_Nd, and ε_Hf to trace provenances for sediments and soils.     

Investigation of thallium fluxes from subaerial volcanism—Implications for the present and past mass balance of thallium in the oceans

A suite of 34 volcanic gas condensates and particulates from Kilauea (Hawaii), Mt. Etna and Vulcano (Italy), Mt. Merapi (Indonesia), White Island and Mt. Nguaruhoe (New Zealand) were analysed for both Tl isotope compositions and Tl/Pb ratios. When considered together with published Tl-Pb abundance data, the measurements provide globally representative best estimates of Tl/Pb = 0.46 ± 0.25 and ε²⁰⁵Tl = −1.7 ± 2.0 for the emissions of subaerial volcanism to the atmosphere and oceans (ε²⁰⁵Tl is the deviation of the ²⁰⁵Tl/²⁰³Tl isotope ratio from NIST SRM 997 isotope standard in parts per 10,000). Compared to igneous rocks of the crust and mantle, volcanic gases were found to have (i) Tl/Pb ratios that are typically about an order of magnitude higher, and (ii) significantly more variable Tl isotope compositions but a mean ε²⁰⁵Tl value that is indistinguishable from estimates for the Earth’s mantle and continental crust. The first observation can be explained by the more volatile nature of Tl compared to Pb during the production of volcanic gases, whilst the second reflects the contrasting and approximately balanced isotope fractionation effects that are generated by partial evaporation of Tl during magma degassing and partial Tl condensation as a result of the cooling and differentiation of volcanic gases.Mass balance calculations, based on results from this and other recent Tl isotope studies, were carried out to investigate whether temporal changes in the volcanic Tl fluxes could be responsible for the dramatic shift in the ε²⁰⁵Tl value of the oceans at ∼55 Ma, which has been inferred from Tl isotope time series data for ferromanganese crusts. The calculations demonstrate that even large changes in the marine Tl input fluxes from volcanism and other sources are unable to significantly alter the Tl isotope composition of the oceans. Based on modelling, it is shown that the large inferred change in the ε²⁰⁵Tl value of seawater is best explained if the oceans of the early Cenozoic featured significantly larger Tl output fluxes to oxic pelagic sediments, whilst the sink fluxes to altered ocean crust remained approximately constant.     

Zircon U-Pb and Hf isotope constraints on crustal melting associated with the Emeishan mantle plume

SHRIMP zircon U-Pb dates, combined with in-situ Hf isotopic data, provide new constraints on the petrogenesis and protolith of peralkaline, metaluminous and peraluminous intrusions and rhyolitic tuffs in the Emeishan large igneous province, with significant bearing on crustal melting associated with mantle plumes. Syenite and A-type granitic intrusions from Huili, Miyi and Taihe in the center of this large igneous province yield U-Pb dates at ∼260 Ma, consistent with the ages obtained for mafic layered intrusions in the same province. Zircon from these rocks exhibits a wide range of initial Hf isotope ratios (ε_Hf(t) = −1.4 to +13.4), with corresponding T_DM1 of 400-900 Ma. The highest ε_Hf(t) value is only marginally lower than that of depleted mantle reservoir at 260 Ma, suggesting that their source is primarily juvenile crust added during Emeishan volcanism, with incorporation of variable amounts of Neoproterozoic crust. The trigger of crustal melting is most likely related to advective heating associated with magmatic underplating. In contrast, the 255-251 Ma peraluminous granites from Ailanghe and 238 Ma rhyolitic tuff from Binchuan, have negative initial ε_Hf values of −1.3 to −4.4, and of −7.7 to −14, respectively. Hf isotopic model ages and presence of inherited zircons indicate their derivation from Mesoproterozoic and Paleoproterozoic crust, respectively. Given the time lag relative to the plume impact (∼260 Ma) and insignificant mantle contribution to 255-238 Ma magmatism, conductive heating is suggested as the trigger of crustal melting that resulted in formation of delayed felsic magmas. The involvement of older crust in younger felsic magmas is consistent with upward heat transfer to the lithosphere during plume impregnation, if the age of crust is inversely stratified, i.e., changes from Paleoproterozoic to Mesoproterozoic to Neoproterozoic to Permian with increasing depth. Such crust may have resulted from episodic, downward crustal growth during the evolution of the western Yangtze Craton.     

海洋Nd同位素演化及古洋流循环示踪研究

海洋Nd同位素演化已经成为示踪陆源风化输入和洋流循环改变的最重要的手段之一,得到了越来越多的应用,并取得了许多重要的成果。海水的Nd同位素组成主要受陆源输入物质控制,热液输入几乎可以忽略。由于Nd在海洋中的停留时间(约500～1000a)略小于海水的平均混合时间(约1500a),且各洋盆有不同的Nd同位素风化输入,因此现代各大洋海水具有不同的Nd同位素组成。在陆源输入稳定的情况下,可以利用海水的Nd同位素组成和演化来示踪水体的混合或洋流循环的改变。目前主要依靠对海洋中水成铁锰结壳、海洋钙质有孔虫壳体、磷酸质鱼骨头或鱼牙齿化石以及沉积物中铁锰氧化物组分等的研究来恢复和反演古海水的Nd同位素组成和演化。4种分析材料各有其优缺点。其中,通过对水成铁锰结壳的Nd同位素分析,基本建立了各大洋新生代以来的主要洋流的Nd同位素组成的长尺度演化。通过有孔虫壳体、鱼化石碎片和沉积物中Fe-Mn氧化物组分可以进行高时间分辨率的古海水Nd同位素演化示踪。利用海水Nd同位素演化可以示踪古洋流通道的开启或闭合,以及获得水体交换的直接信息,为研究构造运动与气候变化之间的关系提供指示。同时,将海水Nd同位素演化与气候变化的指标结合起来,可以用于示踪各种气候条件下洋流循环的改变,将洋流循环的改变与气候变化联系起来,研究两者之间的成因关系。对表层水体的Nd同位素组成的研究则可以示踪不同气候条件下大陆陆源风化输入的改变。     

Comparative behavior of Sr, Nd and Hf isotopic systems during fluid-related deformation at middle crust levels

We have carried out a comparative Rb-Sr, Sm-Nd and Lu-Hf isotopic study of a progressively deformed hercynian leucogranite from the French Massif Central, belonging to the La Marche ductile shear zone, in order to investigate the respective perturbation of these geochronometers with fluid induced deformation. The one-meter wide outcrop presents a strongly deformed and mylonitized zone at the center, and an asymmetric deformation pattern with a higher deformation gradient on the northern side of the zone. Ten samples have been carefully collected every 10 cm North and South away from the strongest deformed mylonitic zone. They have been analyzed for a complete major, trace element data set, oxygen isotopes, Rb-Sr, Sm-Nd and Lu-Hf isotopic systematics.We show that most of major and trace elements except SiO₂, alkaline elements (K₂O, Rb), and some metal transition elements (Cu), are progressively depleted with increasing deformation. This depletion includes REE + Y, but also HFS elements (Ti, Hf, Zr, Nb) which are commonly considered as immobile elements during upper level processes. Variations in elemental ratios with deformation, e.g. decrease in LREE/MREE- HREE, Nd/Hf, Th/Sr, increase in Rb/Sr, U/Th and constant Sr/Nd, lead to propose the following order of element mobility: U ? Th > Sr = Nd ? Hf + HREE. We conclude in agreement with previous tectonic and metallogenic studies that trace element patterns across the shear zone result from circulation of oxidizing F-rich hydrothermal fluids associated with deformation. A temperature of the fluid of 470-480 °C can be deduced from the δ¹⁸O equilibrium between quartz-muscovite pairs.Elemental fractionation induces perturbation of the Rb-Sr geochronometer. The well-defined ⁸⁷Rb/⁸⁶Sr-⁸⁷Sr/⁸⁶Sr correlation gives an apparent age of 294 ± 19 Ma, slightly younger than the 323 ± 4 Ma age of leucogranites in this area. This apparent age is interpreted as dating event of intense deformation and fluid circulation associated with mass transfer, and exhumation of the ductile crust shortly after the leucogranite emplacement. Sm-Nd and Lu-Hf isochron-type diagrams do not define any correlation, because of the low fractionated Sm/Nd and Lu/Hf ratios. Isotopic data demonstrate that only the Lu-Hf geochronometer system is not affected by fluid circulation and gives reliable T_DM age (1.29 ± 0.03 Ga) and ε_Hf signatures. By contrast, the Sm-Nd geochronometer system gives erroneous old T_DM ages of 2.84-4 Ga. There is no positive ε_Nd-ε_Hf correlation, because of decreasing ε_Nd values with deformation at constant ε_Hf values. However, ε_Nd-ε_Hf values remain in the broad ε_Nd-ε_Hf terrestrial array, which strongly indicates that fluid-induced fractionation can contribute to the width of the terrestrial array. The strong ε_Hf negative values of the leucogranite are similar to metasedimentary granulitic xenoliths from the French Massif Central and confirm the generation of the leucogranite by several episodes of reworking of the lower crust.     

Natural fractionation of U/U

The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the ²³⁸U/²³⁵U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferromanganese crusts/nodules and BIFs) of ∼1.3‰, exceeding by far the analytical precision of our method (≈0.06‰, 2SD). U isotopes were analyzed with MC-ICP-MS using a mixed ²³⁶U-²³³U isotopic tracer (double spike) to correct for isotope fractionation during sample purification and instrumental mass bias. The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. Light U isotope compositions (relative to SRM-950a) were observed for manganese crusts from the Atlantic and Pacific oceans, which display δ²³⁸U of −0.54‰ to −0.62‰ and for three of four analyzed Banded Iron Formations, which have δ²³⁸U of −0.89‰, −0.72‰ and −0.70‰, respectively. High δ²³⁸U values are observed for black shales from the Black Sea (unit-I and unit-II) and three Kupferschiefer samples (Germany), which display δ²³⁸U of −0.06‰ to +0.43‰. Also, suboxic sediments have slightly elevated δ²³⁸U (−0.41‰ to −0.16‰) compared to seawater, which has δ²³⁸U of −0.41 ± 0.03‰. Granites define a range of δ²³⁸U between −0.20‰ and −0.46‰, but all analyzed basalts are identical within uncertainties and slightly lighter than seawater (δ²³⁸U = −0.29‰).Our findings imply that U isotope fractionation occurs in both oxic (manganese crusts) and suboxic to euxinic environments with opposite directions. In the first case, we hypothesize that this fractionation results from adsorption of U to ferromanganese oxides, as is the case for Mo and possibly Tl isotopes. In the second case, reduction of soluble U^VI to insoluble U^IV probably results in fractionation toward heavy U isotope compositions relative to seawater. These findings imply that variable ocean redox conditions through geological time should result in variations of the seawater U isotope compositions, which may be recorded in sediments or fossils. Thus, U isotopes might be a promising novel geochemical tracer for paleo-redox conditions and the redox evolution on Earth. The discovery that ²³⁸U/²³⁵U varies in nature also has implications for the precision and accuracy of U-Pb dating. The total observed range in U isotope compositions would produce variations in ²⁰⁷Pb/²⁰⁶Pb ages of young U-bearing minerals of up to 3 Ma, and up to 2 Ma for minerals that are 3 billion years old.     

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.     

Thallium isotopes in early diagenetic pyrite - A paleoredox proxy?

This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ∼183 Ma) are compared with data from Late Neogene (<10 Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment-water interface due to the sulfidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment-water interface.The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate.The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.     

High-precision high field strength element partitioning between garnet, amphibole and alkaline melt from Kakanui, New Zealand

The high field strength elements (HFSE: Zr, Hf, Nb, Ta, and W) are an important group of chemical tracers that are increasingly used to investigate magmatic differentiation processes. Successful modeling of these processes requires the availability of accurate mineral-melt partition coefficients (D). To date, these have largely been determined by ion microprobe or laser ablation-ICP-MS analyses of the run products of high-pressure, high-temperature experiments. Since HFSE are (highly) incompatible, relatively immobile, high-charge, and difficult to ionize, these experiments and their analysis are challenging. Here we explore whether high-precision analyses of natural mineral-melt systems can provide additional constraints on HFSE partitioning.The HFSE concentrations in natural garnet and amphibole and their alkaline host melt from Kakanui, New Zealand are determined with high precision isotope dilution on a multi-collector-ICP-MS. Major and trace element compositions combined with Lu-Hf isotopic systematics and detailed petrographic sample analysis are used to assess mineral-melt equilibrium and to provide context for the HFSE D measurements. The whole-rock nephelinite, ∼1 mm sized amphiboles in the nephelinite, and garnet megacrysts have similar initial Hf isotope ratios with a mean initial ¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282900 ± 0.000026 (2σ). In contrast, the amphibole megacrysts are isotopically distinct (¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282830 ± 0.000011). Rare earth element D values for garnet megacryst-nephelinite melt and ∼1 mm amphibole-nephelinite melt plotted as a function of ionic radii show classic near-parabolic trends that are in excellent agreement with crystal lattice-strain models. These observations are consistent with equilibrium between the whole-rock nephelinite, the ∼1 mm amphibole grains within the nephelinite and the garnet megacrysts.High-precision isotope dilution results for Zr and Hf in garnet (D_Zr = 0.220 ± 0.007 and D_Hf = 0.216 ± 0.005 [2σ]), and for all HFSE in amphibole are consistent with previous experimental findings. However, our measurements for Nb and Ta in garnet (D_Nb = 0.0007 ± 0.0001 and D_Ta = 0.0011 ± 0.0006 [2σ]) show that conventional methods may overestimate Nb and Ta concentrations, thereby overestimating both Nb and Ta absolute D values for garnet by up to 3 orders of magnitude and underestimating D_Nb/D_Ta by greater than a factor of 100. As a consequence, the role of residual garnet in imposing Nb/Ta fractionation may be less important than previously thought. Moreover, garnet D_Hf/D_W = 17 and D_Nb/D_Zr = 0.003 imply fractionation of Hf from W and Nb from Zr upon garnet crystallization, which may have influenced short-lived ¹⁸²Hf-¹⁸²W and ⁹²Nb-⁹²Zr isotopic systems in Hadean time.     

Late Neoarchean reworking of the Mesoarchean crustal remnant in northern Liaoning,North China Craton: A U–Pb–Hf–O–Nd perspective

How the earth's crust formed and evolved during the Precambrian times is one of the key questions to decipher the evolution of the early Earth. As one of the few cratons containing well-preserved Eoarchean to Neoarchean basement on Earth, the North China Craton is an ideal natural laboratory to unravel the early crustal evolution. It is controversial whether the Archean tectonothermal events in this area represents reworking or growth of the continental crust. To solve this issue, we have compelled field-based mapping, zircon U–Pb dating by SHRIMP RG and LA–ICP–MS U–Pb, zircon SHRIMP SI oxygen and LA–MC–ICP–MS Hf isotope, and whole-rock Nd–O isotope analyses from the Archean granitoids in northern Liaoning, North China Craton. On the basis of zircon U–Pb isotopic dating and measured geological section investigation, two distinct magmatic suites as enclaves in the Jurassic granites are recognized, viz. a newly discovered 3.0 Ga crustal remnant and a 2.5 Ga granitoid. The Mesoarchean zircons from the 3.0 Ga granodioritic gneisses exhibit heterogeneous Hf isotopic compositions, with the most radiogenic analysis (ε_Hf(t) = +3.8) following the depleted mantle evolution array and the most unradiogenic ε_Hf(t) extending down to −3.4. This implies that both ancient continental crust at least as old as 3.4 Ga and depleted mantle contributed to the magma source of the protoliths of the Mesoarchean gneisses. The ε_Hf(t) values of the Neoarchean zircons from these gneisses overlap the 3.4–3.0 Ga zircon evolution trend, indicating that the ancient crustal materials have been reworked during the late Neoarchean. The Neoarchean zircons from the 2.5 Ga granitoids have a relatively small variation in the Hf isotope and are mainly plotted in the 3.0–2.8 Ga zircon evolution field. However, taking all the ε_Hf(t) values of the Neoarchean zircons into the consideration, we find that the Hf model age of the Neoarchean zircon does not represent the time of crustal growth or reworking but are artifacts of magma mixing. The interaction between the magmas derived from the ancient crustal materials and the depleted mantle is also supported by zircon O isotopic data and Hf–O isotopic modeling of the Neoarchean granitoids. Both Mesoarchean and late Neoarchean tectonothermal events involved synchronous crustal growth and reworking, which may be applicable to other parts of the world.     

Sr,Nd, and Hf Isotope Composition of Rocks of the Reft Gabbro–Diorite–Tonalite Complex (Eastern Slope of the Middle Urals): Petrological and Geological Implications

This paper reports Rb–Sr and Sm–Nd isotope data on the gabbro–diorite–tonalite rock association of the Reft massif (eastern margin of the Middle Urals) and Lu–Hf isotope data on zircon populations from these rocks. In terms of Nd and Hf isotope composition, the rocks of the studied association are subdivided into two distinctly different groups. The first group consists of gabbros and diorites, as well as plagioclase granites from thin dikes and veins cutting across the gabbros. In terms of ⁴³Nd/¹⁴⁴Nd _i = 0.512518–0.512573 (ε_Nd(T) = +8.6...+9.7) and ¹⁷⁶Hf/¹⁷⁷Hf _i = 0.282961–0.283019 (ε_Hf(T) = +15.9...+17.9), these rocks are practically identical to depleted mantle. Their Nd and Hf model ages show wide variations, but in general are close to their crystallization time. The second group is represented by tonalites and quartz diorites, which compose a large body occupying over half of the massif area. These rocks are characterized by the lower values of ¹⁴³Nd/¹⁴⁴Nd _i = 0.512265–0.512388 (ε_Nd(T) = +3.7...+6.0) and ¹⁷⁶Hf/¹⁷⁷Hf _i = 0.282826–0.282870 (ε_Hf(T) = +11.1...+12.7). The T_DM values of the second group are much (two–three times) higher than their geological age (crystallization time), which indicates sufficiently long crustal residence time of their source. The initial ⁸⁷Sr/⁸⁶Sr in the rocks of both the groups varies from 0.70348 to 0.70495. This is likely explained by the different saturation of melts with fluid enriched in radiogenic Sr. The source of this fluid could be seawater that was buried in a subduction zone with oceanic sediments and released during slab dehydration. Obtained data make it possible to conclude that the formation of the studied gabbro–diorite–tonalite association is a result of spatially and temporally close magma formation processes in the crust and mantle, with insignificant contribution of differentiation of mantle basite magma.     

Temperature and Hf-O isotope correlations of young erupted zircons from Tengchong (SE Tibet): Assimilation fractional crystallization during monotonic cooling

Young zircons from crystal-poor volcanic rocks provide the best samples for the investigations of pre-eruption magmatic processes and for testing a possible relationship between zircon Eu anomalies and crustal thickness. We report trace element chemistry and Hf-O isotope compositions of young zircons from 3 Holocene volcanoes in the Tengchong volcanic field, SE Tibet, in order to provide insights into magma evolution processes and conditions for high-K calc-alkaline volcanic rocks in a post-collisional setting. As decreasing zircon Ti content and falling temperature, zircon Hf content and Yb/Sm increase whereas zircon Eu anomaly and Th/U decrease, indicating fractional crystallization of plagioclase and zircon during magma cooling. More importantly, zircon Hf isotope ratio (ε_Hf values) increases with decreasing zircon Ti content and falling temperature (T), suggesting gradually increasing incorporation of relatively high ε_Hf juvenile materials in the crystallizing zircons during magma evolution. Negative correlations between zircon ε_Hf and zircon δ¹⁸O also support open-system magma evolution. Our data suggest fractional crystallization of a magma with simultaneous contamination by high ε_Hf and low δ ¹⁸O juvenile (immature) crustal materials during monotonic cooling after zircon saturation. The low-T, high-ε_Hf and low- δ ¹⁸O zircons may indicate the involvement of the early Cretaceous juvenile granitic country rocks during shallow magma evolution. Average Eu anomalies in zircons from young Tengchong lavas yield crustal thickness of 40.7 ± 6.8 km, consistent with present crustal thickness (42.5 km) determined by geophysical methods.     

Cadmium isotopic composition in the ocean

The oceanic cycle of cadmium is still poorly understood, despite its importance for phytoplankton growth and paleoceanographic applications. As for other elements that are biologically recycled, variations in isotopic composition may bring unique insights. This article presents (i) a protocol for the measurement of cadmium isotopic composition (Cd IC) in seawater and in phytoplankton cells; (ii) the first Cd IC data in seawater, from two full depth stations, in the northwest Pacific and the northwest Mediterranean Sea; (iii) the first Cd IC data in phytoplankton cells, cultured in vitro. The Cd IC variation range in seawater found at these stations is not greater than 1.5 ε_Cd/amu units, only slightly larger than the mean uncertainty of measurement (0.8 ε_Cd/amu). Nevertheless, systematic variations of the Cd IC and concentration in the upper 300 m of the northwest Pacific suggest the occurrence of Cd isotopic fractionation by phytoplankton uptake, with a fractionation factor of 1.6 ± 1.4 ε_Cd/amu units. This result is supported by the culture experiment data suggesting that freshwater phytoplankton (Chlamydomonas reinhardtii and Chlorella sp.) preferentially take up light Cd isotopes, with a fractionation factor of 3.4 ± 1.4 ε_Cd/amu units. Systematic variations of the Cd IC and hydrographic data between 300 and 700 m in the northwest Pacific have been tentatively attributed to the mixing of the mesothermal (temperature maximum) water (ε_Cd/amu = −0.9 ± 0.8) with the North Pacific Intermediate Water (ε_Cd/amu = 0.5 ± 0.8). In contrast, no significant Cd IC variation is found in the northwest Mediterranean Sea. This observation was attributed to the small surface Cd depletion by phytoplankton uptake and the similar Cd IC of the different water masses found at this site. Overall, these data suggest that (i) phytoplankton uptake fractionates Cd isotopic composition to a measurable degree (fractionation factors of 1.6 and 3.4 ε_Cd/amu units, for the in situ and culture experiment data, respectively), (ii) an open ocean profile of Cd IC shows upper water column variations consistent with preferential uptake and regeneration of light Cd isotopes, and (iii) different water masses may have different Cd IC. This isotopic system could therefore provide information on phytoplankton Cd uptake and on water mass trajectories and mixing in some areas of the ocean. However, the very small Cd IC variations found in this study indicate that applications of Cd isotopic composition to reveal aspects of the present or past Cd oceanic cycle will be very challenging and may require further analytical improvements. Better precision could possibly be obtained with larger seawater samples, a better chemical separation of tin and a more accurate mass bias correction through the use of the double spiking technique.     

Br/Cl ratios and O, H, C, and B isotopic constraints on the origin of saline waters from eastern Canada

Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Cl_molar and δ¹¹B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ¹³C_DIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction.