Lead isotope composition of tree rings as bio-geochemical tracers of heavy metal pollution: a reconnaissance study from Firenze,Italy

Pb isotope composition of tree rings (Celtis Australis) and urban aerosols have been determined to assess whether arboreal species can be used as bio-geochemical tracers of the evolution of heavy metal pollution to the environment. Particular care was paid to setting up a high quality analytical technique to work with arboreal species with low Pb content. The Pb isotope composition of tree rings from 1950 to 1995 is within the range of European aerosols and is correlated with the temporal evolution of Pb isotopes measured in air particulates from Firenze. The entire data set (tree rings and air particulates) demonstrate that Pb isotope composition of tree rings can be used successfully as a proxy of the atmospheric Pb isotope composition of urban areas. This, in turn, suggests that tree rings are potentially a powerful bio-geochemical tracer for monitoring air pollution history due to human activities.     

Comparison of stable carbon and oxygen isotopes in Picea glauca tree rings and Sphagnum fuscum moss remains from subarctic Canada

Stable isotope ratios from tree rings and peatland mosses have become important proxies of past climate variations. We here compare recent stable carbon and oxygen isotope ratios in cellulose of tree rings from white spruce (Picea glauca), growing near the arctic tree line; and cellulose of Sphagnum fuscum stems, growing in a hummock of a subarctic peatland, in west-central Canada. Results show that carbon isotopes in S. fuscum correlate significantly with July temperatures over the past ~20 yr. The oxygen isotopes correlate with both summer temperature and precipitation. Analyses of the tree-ring isotopes revealed summer temperatures to be the main controlling factor for carbon isotope variations, whereas tree-ring oxygen isotope ratios are controlled by a combination of spring temperatures and precipitation totals. We also explore the potential of combining high-frequency (annual) climate signals derived from long tree-ring series with low-frequency (decadal to centennial) climate signals derived from the moss remains in peat deposits. This cross-archive comparison revealed no association between the oxygen isotopes, which likely results from the varying sensitivity of the archives to different seasons. For the carbon isotopes, common variance could be achieved through adjustments of the Sphagnum age model within dating error.     

High‐Precision Sr‐Nd‐Hf‐Pb Isotopic Composition of Chinese Geological Standard Glass Reference Materials CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 by MC‐ICP‐MS and TIMS

To assess the homogeneity of and provide the first Sr‐Nd‐Hf‐Pb isotopic reference values for the Chinese Geological Standard Glasses CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5, we measured these isotopes in several measurement sessions over the course of nearly 3 years. The results were obtained by high‐precision MC‐ICP‐MS and TIMS. Our investigation indicates that these CGSG glass reference materials are homogenous with regard to Sr‐Nd‐Hf‐Pb isotopic distribution and are therefore suitable geochemical materials for Sr‐Nd‐Hf‐Pb isotope measurements. Clear differences in Sr‐Nd‐Hf‐Pb isotopic composition were observed between the glasses and the original powdered rock reference materials (CGSG‐2 and GSR‐7, and especially CGSG‐5 and GSR‐2) because of flux addition during preparation of the glasses. The new Sr‐Nd‐Hf‐Pb isotope data provided here might be useful to the geochemical community for in situ and bulk analysis.     

Application of heavy stable isotopes in forensic isotope geochemistry: A review

Light stable isotopes have been used for many years to characterize the source and transport of materials. More recently heavy isotope systems such as Sr, Nd and Pb have been added to this list in order to aid source identification. With the advent of multiple collector ICP-MS, the range of isotopic tools now available has increased considerably, however, until the isotope systematics of these new non-traditional isotope systems have become better understood, they will not be as useful in characterizing material source and transportation. Applications using heavy metal stable isotopes (mostly traditional heavy isotopes) have reached most avenues in science, including earth sciences, archaeology, anthropology, animal physiology, ecology and toxicology. This field will continue to grow as new applications are developed and techniques become simpler and quicker. This paper provides a review of how this field has grown and presents two new applications using Pb and Sr isotopes in glazes to determine the source of ore used in glazes, and using Sr isotopes to determine the origin of undocumented deceased Mexican border crossers.     

Deep-sea coral aragonite as a recorder for the neodymium isotopic composition of seawater

Deep-sea corals have been shown to be useful archives of rapid changes in ocean chemistry during the last glacial cycle. Their aragonitic skeleton can be absolutely dated by U-Th data, freeing radiocarbon to be used as a water-mass proxy. For certain species of deep-sea corals, the growth rate allows time resolution that is comparable to ice cores. An additional proxy is needed to exploit this opportunity and turn radiocarbon data into rates of ocean overturning in the past.Neodymium isotopes in seawater can serve as a quasi-conservative water-mass tracer and initial results indicate that deep-sea corals may be reliable archives of seawater Nd isotopes. Here we present a systematic study exploring Nd isotopes as a water-mass proxy in deep-sea coral aragonite. We investigated five different genera of modern deep-sea corals (Caryophyllia, Desmophyllum, Enallopsamia, Flabellum, Lophelia), from global locations covering a large potential range of Nd isotopic compositions. Comparison with ambient seawater measurements yields excellent agreement and suggests that deep-sea corals are reliable archives for seawater Nd isotopes.A parallel study of Nd concentrations in these corals yields distribution coefficients for Nd between seawater and coral aragonite of 1-10, omitting one particular genus (Enallopsamia). The corals and seawater did however not come from exactly the same location, and further investigations are needed to reach robust conclusions on the incorporation of Nd into deep-sea coral aragonite.Lastly, we studied the viability of extracting the Nd isotope signal from fossil deep-sea corals by carrying out stepwise cleaning experiments. Our results show that physical removal of the ferromanganese coating and chemical pre-cleaning have the highest impact on Nd concentrations, but that oxidative/reductive cleaning is also needed to acquire a seawater Nd isotope signal.     

The mineral isotope composition of two Precambrian carbonatite complexes from the Kola Alkaline Province – Alteration versus primary magmatic signatures

We investigated the isotope composition (O, C, Sr, Nd, Pb) in mineral separates of the two Precambrian carbonatite complexes Tiksheozero (1.98 Ga) and Siilinjärvi (2.61 Ga) from the Karelian–Kola region in order to obtain information on Precambrian mantle heterogeneity. All isotope systems yield a large range of variations. The combination of cathodoluminescence imaging with stable and radiogenic isotopes on the same samples and mineral separates indicates various processes that caused shifts in isotope systems. Primary isotope signatures are preserved in most calcites (O, C, Sr, Pb), apatites (O, Sr, Nd), amphiboles (O), magnetites (O), and whole rocks (Sr, Nd).

The primary igneous C and O isotope composition is different for both complexes (Tiksheozero: δ¹³C = − 5.0‰, δ¹⁸O = 6.9‰; Siilinjärvi: δ¹³C = − 3.7‰, δ¹⁸O = 7.4‰) but very uniform and requires homogenization of both carbon and oxygen in the carbonatite melt. The lowest Sr isotope ratios of our carbonates and apatites from the Archaean Siilinjärvi (0.70137) and the Palaeoproterozoic Tiksheozero (0.70228) complexes are in the range of bulk silicate earth (BSE). Positive ε_Nd values of the two carbonatites point to very early Archaean enrichment of Sm/Nd in the Fennoscandian mantle. No HIMU components could be detected in the two complexes, whereas Tiksheozero carbonatites give the first indication of Palaeoproterozoic U depletion for Fennoscandia.

Sub-solidus exchange processes with water during emplacement and cooling of carbonatites caused an increase in the oxygen isotope composition of some carbonates and probably also an increase of their ⁸⁷Sr/⁸⁶Sr ratio. A larger increase of initial Sr isotope ratios was found in carbonatized silicic rocks compared to carbonatite bodies. The Svecofennian metamorphic overprint (1.9–1.7 Ga) caused reset of Rb/Sr (mainly mica) and Pb/Pb (mainly apatite) isochron systems.     

Petrogenesis of isotopically unusual Pliocene olivine leucitites from Deep Springs Valley, California

High-K mafic alkalic lavas (5.4 to 3.2 wt% K₂O) from Deep Springs Valley, California define good correlations of increasing incompatible element (e.g., Sr, Zr, Ba, LREE) and compatible element contents (e.g., Ni, Cr) with increasing MgO. Strontium and Nd isotope compositions are also correlated with MgO; ⁸⁷Sr/⁸⁶Sr ratios decrease and ɛ_Nd values increase with decreasing MgO. The Sr and Nd isotope compositions of these lavas are extreme compared to most other continental and oceanic rocks; ⁸⁷Sr/⁸⁶Sr ratios range from 0.7121 to 0.7105 and ɛ_Nd values range from −16.9 to −15.4. Lead isotope ratios are relatively constant, ²⁰⁶Pb/²⁰⁴Pb ∼17.2, ²⁰⁷Pb/²⁰⁴Pb ∼15.5, and ²⁰⁸Pb/²⁰⁴Pb ∼38.6. Depleted mantle model ages calculated using Sr and Nd isotopes imply that the reservoir these lavas were derived from has been distinct from the depleted mantle reservoir since the early Proterozoic. The Sr-Nd-Pb isotope variations of the Deep Springs Valley lavas are unique because they do not plot along either the EM I or EM II arrays. For example, most basalts that have low ɛ_Nd values and unradiogenic ²⁰⁶Pb/²⁰⁴Pb ratios have relatively low ⁸⁷Sr/⁸⁶Sr ratios (the EM I array), whereas basalts with low ɛ_Nd values and high ⁸⁷Sr/⁸⁶Sr ratios have radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios (the EM II array). High-K lavas from Deep Springs Valley have EM II-like Sr and Nd isotope compositions, but EM I-like Pb isotope compositions. A simple method for producing the range of isotopic and major- and trace-element variations in the Deep Springs Valley lavas is by two-component mixing between this unusual K-rich mantle source and a more typical depleted mantle basalt. We favor passage of MORB-like magmas that partially fused and were contaminated by potassic magmas derived from melting high-K mantle veins that were stored in the lithospheric mantle. The origin of the anomalously high ⁸⁷Sr/⁸⁶Sr and ²⁰⁸Pb/²⁰⁴Pb ratios and low ɛ_Nd values and ²⁰⁶Pb/²⁰⁴Pb ratios requires addition of an old component with high Rb/Sr and Th/Pb ratios but low Sm/Nd and U/Pb ratios into the mantle source region from which these basalts were derived. This old component may be sediments that were introduced into the mantle, either during Proterozoic subduction, or by foundering of Proterozoic age crust into the mantle at some time prior to eruption of the lavas. Received: 28 February 1997 / Accepted: 9 July 1998     

Baseline determination of the atmospheric Pb,Sr and Nd isotopic compositions in the Rhine valley,Vosges mountains (France) and the Central Swiss Alps

The Pb, Sr and Nd isotopic compositions of biomonitors (lichen, moss, bark) and soil litter from different regions in the Rhine valley, as well as of <0.45 μm particles separated out of ice of the Rhône and Oberaar glaciers and lichens from the Swiss Central Alps, have been determined in order to deduce the natural baseline of the atmospheric isotopic compositions of these regions, which are suggested to be close to the isotopic compositions of the corresponding basement rocks or soils at the same sites. ²⁰⁶Pb/²⁰⁷Pb and ⁸⁷Sr/⁸⁶Sr isotope ratios are positively correlated. Most polluted samples from traffic-rich urban environments have the least radiogenic Pb and Sr isotopic compositions with ²⁰⁶Pb/²⁰⁷Pb and ⁸⁷Sr/⁸⁶Sr ratios of 1.11 and 0.7094, respectively. These ratios are very different from those of the atmospheric baseline for the Vosges mountains and the Rhine valley (²⁰⁶Pb/²⁰⁷Pb: 1.158–1.167; ⁸⁷Sr/⁸⁶Sr: 0.719–0.725; ε_Nd: −7.5 to −10.1). However, this study indicates that the baseline of the atmospheric natural Pb and Sr isotopic compositions is affected by anthropogenic (traffic, industrial and urban) emissions even in remote areas. Lichen samples from below the Rhône and Oberaar glaciers reflect the baseline composition close to the Grimsel pass in the Central Swiss Alps (⁸⁷Sr/⁸⁶Sr: 0.714 − 0.716; ε_Nd: −3.6 to −8.1). The ¹⁴³Nd/¹⁴⁴Nd isotope ratios are highly variable (8ε units) and it is suggested that the variation of the ¹⁴³Nd/¹⁴⁴Nd is controlled by wet deposition and aerosols originating from the regional natural and industrial urban environments and from more distant regions like the Sahara in North Africa. The least anthropogenetically affected samples collected in remote areas have isotopic compositions closest to those of the corresponding granitoid basement rocks.     

The source of calcium in wet atmospheric deposits: Ca-Sr isotope evidence

Tracing the origin of calcium in wet atmospheric deposits is important for environmental studies since it is a dominant acid neutralising cation and an essential nutrient. Here we present the first calcium isotope ratio measurements for rain and snow. Samples from northeastern and southern locations (France, Switzerland, Luxembourg, California and Japan) suggest a carbonate origin. Only at a local scale in a forested watershed (Vosges mountains, France) the Ca isotopic compositions of rainwater indicate that the rainwater becomes admixed with throughfall solution, which is a mixing product of Ca from dissolved atmospheric dust particles and leave excretions. If this proves to be widely true, the contribution of Ca from the canopy could be very important for the neutralisation of acid rain and of the corresponding soil system in forested watersheds. In such cases Ca and Sr cycles are decoupled in the lower atmosphere. In contrast to Sr isotopes, Ca isotopes can be applied to tracing processes occurring in the biosphere.     

Phlogopite in the generation of olivine-melilitites from Namaqualand, South Africa and implications for element fractionation processes in the upper mantle

Major and trace element and Sr, Nd and Pb isotope analyses are presented for thirteen olivine-melilitites from Namaqualand, South Africa. Major element variations are consistent with derivation from carbonated garnet-peridotite at depths of at least 100 km and trace element abundances indicate melt fractions of 4%. Ubiquitous negative K anomalies and low, buffered K₂O concentrations are interpreted to reflect the effect of residual phlogopite during melting. It is suggested that phlogopite stability and low melt potassium saturation concentrations are enhanced by high CO₂/(CO₂ + H₂O) conditions. Residual phlogopite can also account for low measured Rb/Sr, Ba/Sr and Th/U ratios in the melilitites. REE abundances are controlled by residual garnet and hence Sm/Nd ratios are low (0.13–0.18). U/Pb ratios vary from 0.05 to 5 and are a function of Pb concentration which is in turn controlled by residual Pb-rich phase (probably sulphide). Nd and Sr isotopes are comparable with OIB from St. Helena, although two samples extend to higher ⁸⁷Sr/⁸⁶Sr ratios. Present day Pb isotopes are much more variable and partly reflect radiogenic growth since emplacement as a result of the highly variable U/Pb ratios.

Many of the trace element characteristics of the melilitites are distinct from those of within-plate potassic magmas despite both being derived from phlogopite-bearing, enriched mantle source regions. This can be attributed to the depth at which source enrichment occurred and the subsequent control exerted by phlogopite and carbonate during melting. In contrast to melilitites, potassic magmas are derived from shallower depths under low CO₂/(CO₂ + H₂O) conditions and at higher temperatures at which phlogopite melts more readily.

The incompatible element ratios of the melilitites are also similar to those both observed in HIMU ocean island basalts (OIB) and inferred for HIMU OIB source regions from isotope variations (viz, low Sm/Nd, Rb/Sr, K/Nb, Th/U and high U/Pb and Ce/Pb). It is suggested that HIMU OIB's may be derived from sources that have been subject to enrichment by a melt generated in the presence of residual phlogopite.     

Large fractionation of calcium isotopes during cave-analogue calcium carbonate growth

We have measured δ^44/42Ca of laboratory-precipitated calcite grown in an experimental setup that closely replicates stalagmite formation. Calcium solutions were dripped onto two different substrates in tightly-controlled conditions and calcite precipitated due to rapid CO₂ degassing. With seeded glass slides as the substrate, we observe a Ca isotope ratio in the calcite which is ∼0.5‰ per amu lower than that in the growth solution. This fractionation is generally almost twice that observed in previously published calcite growth experiments and indicates a large kinetic effect on Ca isotopes in the stalagmite growth environment. The precipitate forming near the spot where the drip lands shows slightly greater solution-to-precipitate fractionation than calcite further from the drip reflecting a decrease in this kinetic fractionation as precipitation continues. We interpret these results in the context of the model of Fantle and DePaolo (2007) which involves surface entrapment of light Ca isotopes to decrease calcite δ^44/42Ca, and depletion of Ca from the solution in the direct vicinity of the growing calcite to increase calcite δ^44/42Ca. In the stalagmite setting, the second of these effects is minimized so that calcite Ca isotope ratios are unusually light. This interpretation suggests that stalagmite Ca isotope ratios should decrease with the saturation state of the drip water (i.e. with the growth rate of calcite). Ca isotopes might therefore allow reconstruction of surface entrapment of trace metals and isotopes more generally and might, for instance, allow an assessment of the appropriate relationship between oxygen isotope fractionation and temperature for periods of past growth in stalagmites.     

Geochemistry and petrogenesis of carbonatites from South Nam Xe,Lai Chau area,northwest Vietnam

This paper presents a study of the petrography, mineral chemistry, geochemistry, and Sr–Nd–Pb–C–O isotope systematics of carbonatite dykes and associated rocks from the northeastern part of the Song Da intracontinental rift in South Nam Xe (northwest Vietnam) aimed at constraining the origin of the carbonatite magmas. The carbonatites are characterized by SiO₂ < 12.18 wt.% and by wide ranges in FeO, MgO and CaO content that define them as calciocarbonatite and ferrocarbonatite. On U–Th–Pb isochron diagrams, whole rocks and mineral separates from the ferrocarbonatites form linear arrays corresponding to ages of 30.2–31.6 Ma (Rupelian, Oligocene). The South Nam Xe carbonatites are extremely enriched in Sr, Ba, and light rare earth elements (LREE), and depleted in high field strength elements (HFSE) (e.g. Ti, Nb, Ta, Zr and Hf). The age–corrected Sr–Nd–Pb isotope ratios and C isotope data are relatively uniform (⁸⁷Sr/⁸⁶Sr_(t) = 0.708193–0.708349; ¹⁴³Nd/¹⁴⁴Nd_(t) = 0.512250–0.512267; ε_Nd(t) = ?6.46 to ?6.80; ²⁰⁶Pb/²⁰⁴Pb_(t) = 18.26–18.79; ²⁰⁷Pb/²⁰⁴Pb_(t) = 15.62–15.64; ²⁰⁸Pb/²⁰⁴Pb_(t) = 38.80–39.38; δ¹³C_V-PDB = –2.7?‰ to ?4.1?‰). These isotopic compositions indicate source contamination that occurred before the production of the carbonatite magmas, and did not change noticeably during or after emplacement. The variation in oxygen isotopes is consistent with the change in mineral compositions and trace element abundances: the lower δ¹⁸O values (9.1–11.0?‰) coupled with Sr-rich, Mn-poor calcite, and igneous textures such as triple junctions among calcite grain boundaries, define a magmatic origin. However, the elevated δ¹⁸O values of the ferrocarbonatites (12.0–13.3?‰) coupled with a volatile-bearing mineral assemblages (including REE fluorcarbonates, sulfates, sulfides and fluorite) may be due to interaction with meteoric water during low-temperature alteration. High δ¹³C values and Sr–Pb ratios, and low Rb/Sr (0.00014–0.00301), Sm/Nd (0.089–0.141) and ¹⁴³Nd/¹⁴⁴Nd ratios, coupled with very high Sr-Nd concentrations, suggest the involvement of an enriched mantle component, which probably resulted from metasomatism due to the migration of subducted material. Because of the lack of tectonic data and the limited number of samples studied, this conclusion is still ambiguous and requires further study.     

Sr and Nd isotope data from the fluorspar district of Asturias, northern Spain

The origin and age of the hydrothermal fluids related to the precipitation of fluorite, barite and calcite in the Villabona, La Collada and Berbes localities (Asturias fluorspar district, N Spain) have been evaluated from Sr and Nd radiogenic isotopes. Sr isotope data (⁸⁷Sr / ⁸⁶Sr = 0.7081 to 0.7096) are compatible with mixing between seawater and a more evolved groundwater that interacted with the basement. From Nd isotopes in fluorite, an isochron age of 185 ± 29 Ma (Lower Jurassic) was obtained, consistent with other hydrothermal events in the Iberian Peninsula and Europe. These constraints are essential to proceed with a quantitative model for the genesis of the mineralization that includes fluid and heat flow together with reactive transport of solutes.     

Carbonatite Magmatism and Plume Activity: Implications from the Nd, Pb and Sr Isotope Systematics of Oldoinyo Lengai

New Nd (0.51261–0.51268), Pb (²⁰⁶Pb/²⁰⁴Pb: 19.24–19.26),and Sr (0.70437–0.70446) isotopic compositions from tennatrocarbonatite lavas, collected in June 1993 from OldoinyoLengai, the only known active carbonatite volcano, are relativelyuniform, and are similar to data from the 1960 and 1988 flows.Three of the samples contain silicate spheroids, one of whichhas Nd and Sr isotopic ratios similar to host natrocarbonatite,consistent with an origin by liquid immiscibility or the mixingof melts with similar isotopic compositions. Pb isotope datafor two samples of trona are inconsistent with its involvementin the genesis of natrocarbonatite. New Pb isotope data fromsilicate volcanic and plutonic blocks (ijolite, nephelinite,phonolite, syenite) from Oldoinyo Lengai are highly variable(²⁰⁶Pb/²⁰⁴Pb, 17.75–19.34; ²⁰⁷Pb/²⁰⁴Pb, 15.41–15.67;²⁰⁸Pb/²⁰⁴Pb, 37.79–39.67), and define near-linear arraysin Pb-Pb diagrams. The isotopic data for the silicate rocksfrom Oldoinyo Lengai are best explained by invoking discretepartial melting events which generate undersaturated alkalinesilicate magmas with distinct isotopic ratios. Pb isotope ratiosfrom most ijolites and phonolites are predominantly lower andmore variable than from the natrocarbonatites, and are attributedto interaction between silicate melts involving HIMU and EMIsource components and an additional component, such as lower-crustalgranulites, DMM or PREMA (prevalent mantle). Variations in Nd,Pb and Sr isotope ratios from Oldoinyo Lengai, among the largestyet documented from a single volcano, are attributed to mantlesource heterogeneity involving mainly the mixing of HIMU andEMI mantle components. Based on the new isotopic data from OldoinyoLengai and data from other East African carbonatites, and mantlexenoliths, we propose a two-stage model in an attempt to explainthe isotope variations shown by carbonatites in this area. Themodel involves (I) the release of metasomatizing agents withHIMU-like signatures from upwelling mantle (‘plume’)source, which in turn metasomatize the sub-continental (old,isotopically enriched, EMI-like) lithosphere, and (2) variabledegrees and discrete partial melting of the resulting heterogeneous,metasomatized lithosphere. KEY WORDS: carbonatite; isotopes; Oldoinyo Lengai; mantle plumes ^*Telephone: (613) 788–2660, ext. 4419. Fax: (613) 788–4490. e-mail: kbell{at}ccs.carleton.ca     

Isotopic constraints on age and duration of fluid-assisted high-pressure eclogite-facies recrystallization during exhumation of deeply subducted continental crust in the Sulu orogen

Fluid availability during high‐grade metamorphism is a critical factor in dictating petrological, geochemical and isotopic reequilibration between metamorphic minerals, with fluid‐absent metamorphism commonly resulting in neither zircon growth/recrystallization for U‐Pb dating nor Sm‐Nd isotopic resetting for isochron dating. While peak ultra‐high pressure (UHP) metamorphism is characterized by fluid immobility, high‐pressure (HP) eclogite‐facies recrystallization during exhumation is expected to take place in the presence of fluid. A multichronological study of UHP eclogite from the Sulu orogen of China indicates zircon growth at 216 ± 3 Ma as well as mineral Sm‐Nd and Rb‐Sr reequilibration at 216 ± 5 Ma, which are uniformly younger than UHP metamorphic ages of 231 ± 4 to 227 ± 2 Ma as dated by the SHRIMP U‐Pb method for coesite‐bearing domains of zircon. O isotope reequilibration was achieved between the Sm‐Nd and Rb‐Sr isochron minerals, but Hf isotopes were not homogenized between different grains of zircon. The HP eclogite‐facies recrystallization is also evident from petrography. Thus this process occurred during exhumation with fluid availability from decompression dehydration of hydrous minerals and the exsolution of hydroxyl from nominally anhydrous minerals. This provides significant amounts of internally derived fluid for extensive retrogression within the UHP metamorphosed slabs. Based on available experimental diffusion data, the consistent reequilibration of U‐Pb, Sm‐Nd, Rb‐Sr and O isotope systems in the eclogite minerals demonstrates that time‐scale for the HP eclogite‐facies recrystallization is c. 1.9–9.3 Myr or less. This provides a maximum estimate for duration of the fluid‐facilitated process in the HP eclogite‐facies regime during the exhumation of deeply subducted continental crust.     

Plume-related mantle source of super-large rare metal deposits from the Lovozero and Khibina massifs on the Kola Peninsula, Eastern part of Baltic Shield: Sr, Nd and Hf isotope systematics

The two world’s largest complexes of highly alkaline nepheline syenites and related rare metal loparite and eudialyte deposits, the Khibina and Lovozero massifs, occur in the central part of the Kola Peninsula. We measured for the first time in situ the trace element concentrations and the Sr, Nd and Hf isotope ratios by LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometer) in loparite, eudialyte an in some other pegmatitic minerals. The results are in aggreement with the whole rock Sr and Nd isotope which suggests the formation of these superlarge rare metal deposits in a magmatic closed system. The initial Hf, Sr, Nd isotope ratios are similar to the isotopic signatures of OIB indicating depleted mantle as a source. This leads to the suggestion that the origin of these gigantic alkaline intrusions is connected to a deep seated mantle source—possibly to a lower mantle plume. The required combination of a depleted mantle and high rare metal enrichment in the source can be explained by the input of incompatible elements by metasomatising melts/fluids into the zones of alkaline magma generation shortly before the partial melting event (to avoid ingrowth of radiogenic isotopes). The minerals belovite and pyrochlore from the pegmatites are abnormally high in ⁸⁷Sr /⁸⁶Sr ratios. This may be explained by closed system isotope evolution as a result of a significant increase in Rb/Sr during the evolution of the peralkaline magma.     

Tracing element sources of hydrothermal mineral deposits: REE and Y distribution and Sr-Nd-Pb isotopes in fluorite from MVT deposits in the Pennine Orefield,England

Fluorite from Mississippi Valley Type (MVT) deposits in the South Pennine Orefield, England, displays significantly different distributions of rare earths and yttrium (REY) compared to fluorite from similar MVT deposits in the North Pennine Orefield. Samples from the South Pennine Orefield display negative Ce and positive Gd and Y anomalies but lack any Eu anomaly, indicating that the REY were mobilized from relatively pure marine sedimentary carbonates. In marked contrast, fluorite from the North Pennine Orefield lacks any Ce and Gd anomalies but shows a pronounced positive Eu anomaly, suggesting that the REY were provided by different source rock(s), that the mineralizing hydrothermal fluid had experienced higher temperatures prior to fluorite precipitation, and that it was derived from deeper crustal levels in the north compared to the south. The isotopic composition of Sr in Blue John fluorite from the South Pennine Orefield suggests that Sr was mobilized from Lower Carboniferous (Tournaisian) limestones, whereas Pb isotopes suggest that in contrast to REY and Sr, Pb was derived from aluminosilicate rocks. Neither Nd nor Sr or Pb isotopes can be used to radiometrically date the formation of Blue John fluorite. All isotope systems studied indicate that the limestone host rock of this fluorite mineralization did not contribute to the trace element budget of the hydrothermal fluid. Our results show that different solutes in a natural water (hydrothermal fluid, groundwater, etc.) may be derived from different sources, and that the study of a small set of elements or isotope ratios may not provide full insight into the genesis or history of a mineralization or a hydrothermal fluid. Our data provide evidence for the uncoupling of Sr, Nd and Pb during fluid-rock interaction and fluid migration, and show that the use of plots such as ⁸⁷Sr/⁸⁶Sr vs. _Nd. to learn about mixing relationships (as is commonly done in igneous geochemistry) is unreliable when applied to natural waters and their precipitates.Editorial handling: B. Lehmann     

Paleoproterozoic volcanic rocks in the southern margin of the North China Craton,central China:Implications for the Columbia supercontinent

The volcanic rocks of the Xiong'er Group are situated in the southern margin of the North China Craton(NCC).Research on the Xiong er Group is important to understand the tectonic evolution of the NCC and the Columbia supercontinent during the Paleoproterozoic.In this study,to constrain the age of the Xiong'er volcanic rocks and identify its tectonic environment,we report zircon LA-ICP-MS data with Hf isotope,whole-rock major and trace element compositions and Sr-Nd-Pb-Hf isotopes of the volcanic rocks of the Xiong'er Group.The Xiong'er volcanic rocks mainly consist of basaltic andesite,andesite.dacite and rhyolite,with minor basalt.Our new sets of data combined with those from previous studies indicate that Xiong'er volcanism should have lasted from 1827 Ma to 1746 Ma as the major phase of the volcanism.These volcanics have extremely low MgO.Cr and Ni contents,are enriched in LREEs and LILEs but depleted in HFSEs(Nb,Ta,and Ti),similar to arc-related volcanic rocks.They are characterized by negative zircon ε_(Hf)_(t) values of-17.4 to 8.8,whole-rock initial ~(87)Sr/~(86)Sr values of 0.7023 to 0.7177 andε_(Nd)(t) values of-10.9 to 6.4.and Pb isotopes(~(206)Pb/~(204)Pb =14.366-16.431,~(207)Pb/~(204)Pb =15.106-15.371,~(208)Pb/~(204)Pb= 32.455-37.422).The available elemental and Sr-Nd-Pb-Hf isotope data suggest that the Xiong'er volcanic rocks were sourced from a mantle contaminated by continental crust.The volcanic rocks of the Xiong'er Group might have been generated by high-degree partial melting of a lithospheric mantle that was originally modified by oceanic subduction in the Archean.Thus,we suggest that the subduction-modified lithospheric mantle occurred in an extensional setting during the breakup of the Columbia supercontinent in the Late Paleoproterozoic,rather than in an arc setting.     

Geochemical trends across an arc-continent collision zone: magma sources and slab-wedge transfer processes below the Pantar Strait volcanoes, Indonesia

Four volcanoes in the Pantar Strait, the westernmost part of the extinct sector of the east Sunda arc, show remarkable across-arc variation in elemental abundances (K₂O: 1.2 to 4.3%), trace element ratios (Pb/Ce: 0.4 to 0.18; Ce/Yb: 20 to 55) and isotope ratios (¹⁴³Nd/¹⁴⁴Nd: 0.51263 to 0.51245; ⁸⁷Sr/⁸⁶Sr: 0.7053 to 0.7068; ²⁰⁶Pb/²⁰⁴Pb: 19.29 to 19.15). Pb isotopes are decoupled from Sr and Nd isotopes, with the frontal volcanoes showing the higher Nd and Pb and lower Sr isotopic ratios. The isotopic and trace element ratios of the volcanic samples are best explained by modification of a MORB-type source (with Indian Ocean island basalt-type Pb isotopic characteristics) by a fluid and a partial melt of subducted continental material (SCM). The frontal volcano contains the highest proportion of the fluid component, with a small contribution of partial melt. The source of the rear-arc volcano is strongly influenced by a partial melt of SCM that had undergone a previous dehydration event, by which it lost most of its fluid-mobile elements such as Pb. The SCM partial melt was in equilibrium with both rutile and garnet, whereas mantle melting took place in the presence of residual mica. The relatively large across-arc increase in incompatible elements can be explained by a combination of increasing addition of SCM partial melt, changing mantle wedge fertility and smaller degrees of partial melting toward the rear of the arc. Comparison with a more westerly across-arc transect shows that the relatively low ¹⁴³Nd/¹⁴⁴Nd ratios of the frontal volcano, and the decoupling of Pb from Sr and Nd isotopes are unique to the Pantar Strait volcanoes. This is likely to reflect magma generation in a collisional environment, where the leading edge of the Australian continent, rather than subducted sediment, contributes to the magma source.     

Geochemical Characteristics and Genesis of the Luxi-Xianrenzhang Diabase Dikes in Xiazhuang Uranium Orefield, Northern Guangdong Province

The Luxi-Xianrenzhang diabase dikes were emplaced into the eastern part of the Guidong composite granitoids in northern Guangdong Province at the end of the Early Cretaceous. They show tholeiitic features, enrichment in large ion lithophile elements, slight enrichment in light rare earth elements, depletion in Zr and Hf, and basically no depletion in Nb and Ta and no Eu anomaly. They are similar to intraplate basalt in terms of trace element characteristics. They have high εNd（t） values （3.6-4.9）, initial ^87Sr/^86Sr ratios （0.70530-70641） and δ^18O values and Dupal anomaly of Pb isotope compositions. Their Sr-Nd, Pb-Sr, Pb-Nd and Pb-Pb isotopes plot between DMM and EMII, with Pb similar to EMII, Nd relatively close to DMM and Sr in between. This profile suggests that the diabase dikes studied were derived from partial melting of a mantle source that had been subjected to metasomatism by fluids originated from a subduction zone under a tectonic environment of crustal extension and lithosphere thinning in the late Yanshanian.