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1.
The hafnium isotope composition of Pacific Ocean water   总被引：1，自引：0，他引：1  
The first Hf isotope data for seawater are reported for a series of stations in the Northwestern Pacific and define a range from εHf = 3.5 ± 1.4 to 8.6 ± 1.6. Most samples have values within error of the average of εHf = 5.9, but significant variations are found in intermediate waters at a depth of 600 m, as well as in deep waters. The Nd and Hf isotope compositions of the deep waters fall within the range of values found for surfaces of hydrogenetic ferromanganese crusts in the region, confirming that Hf in the Fe-Mn crusts has been derived from the overlying water column, which thus provide an archive of past seawater compositions. Although the seawater samples are generally close to the global εNd-εHf correlation obtained from ferromanganese crusts, there are significant deviations from this correlation indicating that there is some additional decoupling between Nd and Hf isotope signals, most likely caused by local water mass mixing and differences in residence times. This is not resolved in the crust samples, which integrate seawater signals over 104 years. The combined use of these two isotope systems in seawater therefore provides an additional dimension for tracing water masses in the oceans. Studies of the distribution of oceanic Hf isotope compositions that have been confined to deep water and boundary waters, as recorded in seafloor ferromanganese crusts, can now be extended and aimed at characterising the entire present-day water column. Average Hf concentrations measured in this study are somewhat lower than previously reported, suggesting a shorter residence time for Hf in the global oceans, although the uncertainty in the extent of Hf removal from the water column during estuarine mixing as well as a lack of data on hydrothermal and dust inputs remains a limit on how well the residence time can be defined.  相似文献   

2.
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 εHf = −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 εHf 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.  相似文献   

3.
The distribution of neodymium isotopes in Arctic Ocean basins   总被引：1，自引：0，他引：1  
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 εNd = −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 εNd = −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 (εNd ∼ −10.5), but have created distinctive Nd isotope signatures that were found near the margin of the Canada Basin (with εNd ∼ −9.0). The deep waters of the Amundsen Basin are also distinct from the Atlantic waters (with εNd = −12.3), indicating that there has been limited inflow from the adjacent Makarov Basin through the Lomonosov Ridge.  相似文献   

4.
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, εHf = 1.55 × εNd + 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 (εHf = 1.36 × εNd + 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.  相似文献   

5.
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 εNd and εHf both decrease with water depth. Similarly, εNd and εHf 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.  相似文献   

6.
The neodymium concentration, CNd, and isotopic composition, εNd, 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 (CNd = 15.5 pmol/kg and εNd = −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 CNd in the surface waters above 150 m, in the Fram Strait inflow branch is higher by a factor of 2 and the εNd is shifted to lower values (−11.8).In the stratified Nansen Basin, where cold low salinity water overlies warmer Atlantic water the CNd and εNd 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 CNd in the surface waters above 150 m, and a higher εNd (−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.  相似文献   

7.
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 εNd values at depths of 800-1000 m (εNd = −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 εNd 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 εNd 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.  相似文献   

8.
We present the first comprehensive set of dissolved 10Be and 9Be concentrations in surface waters and vertical profiles of all major sub-basins of the Arctic Ocean, which are complemented by data from the major Arctic rivers Mackenzie, Lena, Yenisey and Ob. The results show that 10Be and 9Be concentrations in waters below 150 m depth are low and only vary within a factor of 2 throughout the Arctic Basin (350-750 atoms/g and 9-15 pmol/kg, respectively). In marked contrast, Be isotope compositions in the upper 150 m are highly variable and show systematic variations. Cosmogenic 10Be concentrations range from 150 to 1000 atoms/g and concentrations of terrigenous 9Be range from 7 to 65 pmol/kg, resulting in 10Be/9Be ratios (atom/atom) between 0.5 and 14 × 10−8. Inflowing Atlantic water masses in the Eurasian Basin are characterized by a 10Be/9Be signature of 7 × 10−8. The inflow of Pacific water masses across the Bering Strait is characterized by lower ratios of 2-3 × 10−8, which can be traced into the central Arctic Ocean, possibly as far as the Fram Strait. A comparison of the high dissolved surface 10Be and 9Be concentrations (corresponding to low 10Be/9Be signatures of ∼2 × 10−8) in the Eurasian Basin with hydrographic parameters and river data documents efficient and rapid transport of Be with Siberian river waters across the Siberian Arctic shelves into the central Arctic Basin, although significant loss and exchange of Be on the shelves occurs. In contrast, fresh surface waters from the Canada Basin also show high cosmogenic 10Be contents, but are not enriched in terrigenous 9Be (resulting in high 10Be/9Be signatures of up to 14 × 10−8). This is explained by a combination of efficient scavenging of Be in the Mackenzie River estuary and the shelves and additional supply of cosmogenic 10Be via atmospheric fallout and melting of old sea ice. The residence time of Be in the deep Arctic Ocean estimated from our data is 800 years and thus similar to the average Be residence time in the global ocean.  相似文献   

9.
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 εSr 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 εSr 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 εNd and εHf of the saprolites drift only 0–2.6 and 0–3.7 away from the parent rocks, respectively. The negative drifts of the εNd and εHf are coupled with Nd and Hf losses in the saprolites; i.e., larger proportions of Nd and Hf loss correspond to lower εNd and εHf. 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 εNd and εHf 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 εNd and εHf 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 εHf values at a given εNd value, and the regression line between these εNd and εHf 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 εNd and εHf correlation. Our results also indicate that caution is needed when using εSr, εNd, and εHf to trace provenances for sediments and soils.  相似文献   

10.
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 TDM age (1.29 ± 0.03 Ga) and εHf signatures. By contrast, the Sm-Nd geochronometer system gives erroneous old TDM ages of 2.84-4 Ga. There is no positive εNd-εHf correlation, because of decreasing εNd values with deformation at constant εHf values. However, εNd-εHf values remain in the broad εNd-εHf terrestrial array, which strongly indicates that fluid-induced fractionation can contribute to the width of the terrestrial array. The strong εHf 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.  相似文献   

11.
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 (εHf(t) = −1.4 to +13.4), with corresponding TDM1 of 400-900 Ma. The highest εHf(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 εHf 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.  相似文献   

12.
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 (εHf(t) = +3.8) following the depleted mantle evolution array and the most unradiogenic εHf(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 εHf(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 εHf(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.  相似文献   

13.
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 ε114/110Cd (2 SD), based on measurements that each consumed about ∼8 ng of natural Cd (ε114/110Cd 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 ε114/110Cd (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 ε114/110Cd = 3.2 ± 1.0. In contrast, Cd-depleted seawater from the upper water column of the Atlantic and Arctic Oceans displayed isotope compositions of ε114/110Cd = 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.  相似文献   

14.
We have carried out a Pb double-spike and Lu-Hf isotope study of clinopyroxenes from spinel-facies mantle xenoliths entrained in Cenozoic intraplate continental volcanism of the French Massif Central (FMC). U-Th-Pb and Lu-Hf isotope systematics verify the existence of different lithospheric domains beneath the northern and southern FMC. Northern FMC clinopyroxenes have extreme Lu/Hf ratios and ultra-radiogenic Hf (εHf = +39.6 to +2586) that reflect ∼15-25% partial melting in Variscan times (depleted mantle model ages ∼360 Ma). Zr, Hf and Th abundances in these clinopyroxenes are low and unaffected by hydrous/carbonatitic metasomatism that overprinted LILE and light REE abundances and caused decoupling of Lu/Hf-Sm/Nd ratios and Nd-Hf isotopes (εNd = +2.1 to +91.2). Pb isotopes of northern FMC clinopyroxenes are radiogenic (206Pb/204Pb > 19), and typically more so than the host intraplate volcanic rocks. 238U/204Pb ratios range from 17 to 68, and most samples have distinctively low 232Th/238U (<1) and 232Th/204Pb (3-22). Clinopyroxenes from southern FMC lherzolites are generally marked by overall incompatible trace element enrichment including Zr, Hf and Th abundances, and have Pb isotopes that are similar to or less radiogenic than the host volcanic rocks. Hf isotope ratios are less radiogenic (εHf = +5.4 to +41.5) than northern FMC mantle and have been overprinted by silicate-melt-dominated metasomatism that affected this part of FMC mantle. Major element and Lu concentrations of clinopyroxenes from southern FMC harzburgites are broadly similar to northern FMC clinopyroxenes and suggest they experienced similar degrees of melt extraction as northern FMC mantle. 238U/204Pb (53-111) and 232Th/204Pb ratios (157-355) of enriched clinopyroxenes from the southern FMC are extreme and significantly higher than the intraplate volcanic rocks. In summary, mantle peridotites from different parts of the FMC record depletion at ∼360 Ma during Variscan subduction, followed by differing styles of enrichment. Northern FMC mantle was overprinted by a fluid/carbonatitic metasomatic agent that carried elements like U, Pb, Sr and light REE. In contrast, much of the southern FMC mantle was metasomatised by a small-degree partial silicate melt resulting in enrichment of all incompatible trace elements. The extreme mantle 238U/204Pb (northern and southern FMC), 232Th/238U (northern FMC) and 232Th/204Pb ratios (southern FMC), coupled with unremarkable present-day Pb isotope ratios, constrain the timing of enrichment. Mantle metasomatism is a young feature related to melting of the upwelling mantle responsible for Cenozoic FMC volcanism, rather than subduction-related metasomatism intimately associated with mantle depletion during the Variscan orogeny. The varying metasomatic styles relate to pre-existing variations in the thickness of the continental lithospheric lid, which controlled the extent to which upwelling mantle could ascend and melt. In the northern FMC, a thicker and more refractory lithospheric lid (?80 km) only allowed incipient degrees of melting resulting in fluid/carbonatitic metasomatism of the overlying sub-continental lithospheric mantle. The thinner lithospheric lid of the southern FMC (?70 km) allowed larger degrees of melting and resulted in silicate-melt-dominated metasomatism, and also focused the location of the volcanic fields of the FMC above this region.  相似文献   

15.
Subcalcic, high-Cr (G10) garnets are found as inclusions within diamonds and in peridotitic xenoliths. The strong spatial associations between G10 garnets and diamond make them an important tool in the investigation of diamond genesis. We present an integrated study of the major and trace element composition and oxygen-Sr-Nd-Hf isotopic ratios of eight G10 garnets from the Ekati mine (NWT-Canada) and four from the Murowa mine (Zimbabwe) in an attempt to determine their petrogenetic evolution and to further examine a possible relationship between the metasomatic agents responsible for G10 garnet signatures and diamond forming fluids.All garnets display sinusoidal to mildly sinusoidal REE patterns and have negative Ti, Sr and positive U anomalies. They have variably radiogenic 87Sr/86Sr (0.703261-0.731191) and non-radiogenic εNd values (−8.1 to −27.1), except for one sample from Murowa that has a positive εNd of 2.5. One Ekati sample has an extremely low εHf value of −61.6. The Ekati garnets we have studied all appear to come from a single depth in the Slave lithospheric mantle. On the base of Cr-Ca relations they have crystallized at 4.9 GPa and display dunitic Ca intercept values. Their δ18O values range between +5.23‰ and +5.42‰.The Ekati G10 garnets record a complex, multi-stage metasomatic history involving the interaction of several components during their genesis. One metasomatic agent was enriched in HFSE, LREE, Sr, and depleted in Nb. This agent had the least radiogenic Sr. Another metasomatic agent had highly radiogenic Sr, and was enriched in LREE, Sr, Nb, Th and U.The G10 garnets have very low εNd and εHf values combined with radiogenic Sr, thus, they require an early lithospheric mantle enrichment event at some stage during their genesis or during the evolution of any precursor material that they formed from. The only Hf isotope composition measurable from the Ekati suite is so unradiogenic (εHf = −61) that it yields a Lu/Hf model age of 3521 Ma. This indicates that the lithospheric enrichment event seen by the Ekati garnets or their precursors may have occurred in the early stages of the craton stabilization, during the diamond forming event [Westerlund K., Shirey S., Richardson S., Carlson R., Gurney J. and Harris J. (2006) A subduction wedge origin for Paleoarchean peridotitic diamonds and harzburgites from the Panda kimberlite, Slave craton: evidence from Re-Os isotope systematics. Contrib. Mineral. Petrol.152(3), 275-294]. Although our data cannot unequivocally discriminate between a variety of models for the genesis of subcalcic garnets it is clear that the host peridotite originated via melting at shallow depths followed by subduction and that the observed geochemical fingerprint of the garnets is strongly influenced by diamond forming fluids. Diamond forming fluids sampled from fibrous diamonds, have steep REE patterns, negative Ti and Sr anomalies and very low Sm/Nd ratios that are very similar to G10 garnet characteristics. These diamond forming fluids have been recently shown to have extreme Sr and Nd isotopic compositions [Klein-BenDavid O., Pearson D. G., Nowell G. M. and Cantigny P. (2008) Origins of diamond forming fluids—constraints from a coupled Sr-Nd isotope and trace element approach. Extended abstracts to the 9th International Kimberlite Conference, Frankfurt, Germany, 9IKC-A-00118.] that are closely concordant with G10 garnets. The fluids are also rich in LREE, P, K and water, sharing these features with mica-rich metasomes. These similarities suggest that ancient lithospheric metasomes could either provide a source region for, or be a product of diamond forming fluids. Diamond forming fluids appear to be intimately involved in the evolution of G10 garnets in the lithospheric mantle, either acting as a metasomatic agent, or being integral to triggering or enhancing garnet growth in a Cr-rich protolith. Such a link explains the strong association between G10 garnets and diamonds.  相似文献   

16.
In this paper, we present zircon U–Pb age and Hf isotope data to document the significance of magma mixing in the formation of Late Jurassic granitoid intrusions in the eastern Qinling Orogen, China. The Muhuguan granitoid pluton from this orogen consists of monzogranite and lesser biotite granite and granodiorite, all containing abundant hornblende-rich cumulates, dioritic xenoliths, and mafic magmatic enclaves (MMEs). The monzogranite and granodiorite are intruded by a number of lamprophyre dykes. Both a cumulate and a dioritic xenolith samples have concordant zircon U–Pb ages of ca. 161 ± 1 Ma, but possess contrasting Hf isotopic compositions. The cumulate has more radiogenic zircon Hf isotopes with negative ε Hf(t) values (?7.9 to ?2.5) and T DM1 ages of 0.9–1.1 Ga, indicating its derivation likely from basaltic rocks of the Neoproterozoic to early Paleozoic Kuanping Group in the area. The dioritic xenolith has much lower zircon ε Hf(t) values of ?19.5 to ?8.8 and T DM2 ages of 2.4–1.7 Ga, consistent with a juvenile Paleoproterozoic crust source presumably represented by the metabasic rocks of the Qinling Group in the area. Individual samples of the monzogranite, MME, and a lamprophyre dyke have U–Pb ages of 150 ± 1, 152 ± 1, and 152 ± 1 Ma, respectively, demonstrating coeval mafic and felsic magmatism in the Late Jurassic. The lamprophyre dyke has homogeneous, highly negative zircon ε Hf(t) values (?29.8 to ?24.8) and Archean T DM2 ages (3.0–2.7 Ga), and its genesis is interpreted as partial melting of an ancient enriched subcontinental mantle source. Zircons from the fine-grained MME show a large range of ε Hf(t) between ?29.1 and ?9.8, overlapping values of the monzogranite and lamprophyre dyke samples. Zircon U–Pb age and Hf isotopes of the MMEs are consistent with their formation by mixing of crustal- and enriched mantle-derived magmas. The main group of zircons from the monzogranite has ε Hf(t) values (?17.9 to ?9.3) and T DM2 ages (2.3–1.8 Ga) that are compatible with the dioritic xenoliths, indicating that the former was produced by partial melting of Paleoproterozoic crustal source with involvement of mantle-derived magmas. Mafic magmatism revealed from the Muhuguan pluton indicates that the eastern Qinling Orogen was dominated by lithospheric extension during the Late Jurassic. Compilation of existing geological and geochronological data suggests that this extensional event started in Late Jurassic (ca. 160 Ma) and persisted into the Early Cretaceous until ca. 110 Ma. The Jura-Cretaceous extension may have resulted from the late Mesozoic westward subduction of the Pacific plate beneath the East Asian continental margin.  相似文献   

17.
Cadmium isotopic composition in the ocean   总被引：1，自引：0，他引：1  
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 εCd/amu units, only slightly larger than the mean uncertainty of measurement (0.8 εCd/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 εCd/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 εCd/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 (εCd/amu = −0.9 ± 0.8) with the North Pacific Intermediate Water (εCd/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 εCd/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.  相似文献   

18.
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 (DZr = 0.220 ± 0.007 and DHf = 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 (DNb = 0.0007 ± 0.0001 and DTa = 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 DNb/DTa 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 DHf/DW = 17 and DNb/DZr = 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.  相似文献   

19.
Several I- and A-type granite, syenite plutons and spatially associated, giant Fe-Ti-V deposit-bearing mafic-ultramafic layered intrusions occur in the Pan-Xi (Panzhihua-Xichang) area within the inner zone of the Emeishan large igneous province (ELIP). These complexes are interpreted to be related to the Emeishan mantle plume. We present LA-ICP-MS and SIMS zircon U-Pb ages and Hf-Nd isotopic compositions for the gabbros, syenites and granites from these complexes. The dating shows that the age of the felsic intrusive magmatism (256.2 ± 3.0-259.8 ± 1.6 Ma) is indistinguishable from that of the mafic intrusive magmatism (255.4 ± 3.1-259.5 ± 2.7 Ma) and represents the final phase of a continuous magmatic episode that lasted no more than 10 Myr. The upper gabbros in the mafic-ultramafic intrusions are generally more isotopically enriched (lower εNd and εHf) than the middle and lower gabbros, suggesting that the upper gabbros have experienced a higher level of crustal contamination than the lower gabbros. The significantly positive εHf(t) values of the A-type granites and syenites (+4.9 to +10.8) are higher than those of the upper gabbros of the associated mafic intrusion, which shows that they cannot be derived by fractional crystallization of these bodies. They are however identical to those of the mafic enclaves (+7.0 to +11.4) and middle and lower gabbros, implying that they are cogenetic. We suggest that they were generated by fractionation of large-volume, plume-related basaltic magmas that ponded deep in the crust. The deep-seated magma chamber erupted in two stages: the first near a density minimum in the basaltic fractionation trend and the second during the final stage of fractionation when the magma was a low density Fe-poor, Si-rich felsic magma. The basaltic magmas emplaced in the shallow-level magma chambers differentiated to form mafic-ultramafic layered intrusions accompanied by a small amount of crustal assimilation through roof melting. Evolved A-type granites (synenites and syenodiorites) were produced dominantly by crystallization in the deep crustal magma chamber. In contrast, the I-type granites have negative εNd(t) [−6.3 to −7.5] and εHf(t) [−1.3 to −6.7] values, with the Nd model ages () of 1.63−1.67 Ga and Hf model ages () of 1.56−1.58 Ga, suggesting that they were mainly derived from partial melting of Mesoproterozoic crust. In combination with previous studies, this study also shows that plume activity not only gave rise to reworking of ancient crust, but also significant growth of juvenile crust in the center of the ELIP.  相似文献   

20.
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 (εNd(T) = +8.6...+9.7) and 176Hf/177Hf i = 0.282961–0.283019 (εHf(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 (εNd(T) = +3.7...+6.0) and 176Hf/177Hf i = 0.282826–0.282870 (εHf(T) = +11.1...+12.7). The TDM 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.  相似文献   

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