Correlation of δ<Superscript>18</Superscript>O and initial<Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr ratios in Kirkpatrick basalt on Mt. Falla,transantarctic mountains

Theδ¹⁸O (SMOW) values of the Kirkpatrick Basalt (Jurassic) on Mt. Falla, Queen Alexandra Range, vary between +6.3‰ and +8.6‰ The apparent enrichment of these rocks in¹⁸O excludes the possibility that they were altered by interaction with aqueous solutions of meteoric origin. Theδ¹⁸O values of the flows correlate significantly with the initial⁸⁷Sr/⁸⁶Sr ratios and all major elements. These correlations confirm the hypothesis that the basalt magma was contaminated by rocks of the continental crust through which it was extruded. Estimates of the chemical composition of the basalt magma and the contaminant, based on extrapolations of the new oxygen data, generally confirm earlier estimates based on extrapolations of initial⁸⁷Sr/⁸⁶Sr ratios. The⁸⁷Sr/⁸⁶Sr ratio of the uncontaminated basalt was 0.7093 which indicates that magma may have originated by melting either in old Rb-enriched lithospheric mantle under Antarctica or in the overlying crust, or both.     

An <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar,Rb/Sr,and stable isotope study of micas in low-grade fold-and-thrust belt: an example from the Swiss Helvetic Alps

White micas in carbonate-rich tectonites and a few other rock types of large thrusts in the Swiss Helvetic fold-and-thrust belt have been analyzed by ⁴⁰Ar/ ³⁹Ar and Rb/Sr techniques to better constrain the timing of Alpine deformation for this region. Incremental ⁴⁰Ar/ ³⁹Ar heating experiments of 25 weakly metamorphosed (anchizone to low greenschist) samples yield plateau and staircase spectra. We interpret most of the staircase release spectra result from variable mixtures of syntectonic (neoformed) and detrital micas. The range in dates obtained within individual spectra depends primarily on the duration of mica nucleation and growth, and relative proportions of neoformed and detrital mica. Rb/Sr analyses of 12 samples yield dates of ca. 10–39 Ma (excluding one anomalously young sample). These dates are slightly younger than the ⁴⁰Ar/ ³⁹Ar total gas dates obtained for the same samples. The Rb/Sr dates were calculated using initial ⁸⁷Sr/ ⁸⁶Sr ratios obtained from the carbonate-dominated host rocks, which are higher than normal Mesozoic carbonate values due to exchange with fluids of higher ⁸⁷Sr/ ⁸⁶Sr ratios (and lower ¹⁸O/ ¹⁶O ratios). Model dates calculated using ⁸⁷Sr/ ⁸⁶Sr values typical of Mesozoic marine carbonates more closely approximate the ⁴⁰Ar/ ³⁹Ar total gas dates for most of the samples. The similarities of Rb/Sr and ⁴⁰Ar/ ³⁹Ar total gas dates are consistent with limited amounts of detrital mica in the samples. The d ¹⁸O values range from 24–15‰ (VSMOW) for 2–6 µm micas and 27–16‰ for the carbonate host rocks. The carbonate values are significantly lower than their protolith values due to localized fluid-rock interaction and fluid flow along most thrust surfaces. Although most calcite-mica pairs are not in oxygen isotope equilibrium at temperatures of ca. 200–400 °C, their isotopic fractionations are indicative of either 1) partial exchange between the minerals and a common external fluid, or 2) growth or isotopic exchange of the mica with the carbonate after the carbonate had isotopically exchanged with an external fluid. The geological significance of these results is not easily or uniquely determined, and exemplifies the difficulties inherent in dating very fine-grained micas of highly deformed tectonites in low-grade metamorphic terranes. Two generalizations can be made regarding the dates obtained from the Helvetic thrusts: 1) samples from the two highest thrusts (Mt. Gond and Sublage) have all of their ⁴⁰Ar/ ³⁹Ar steps above 20 Ma, and 2) most samples from the deepest Helvetic thrusts have steps (often accounting for more than 80% of ³⁹Ar release) between 15 and 25 Ma. These dates are consistent with the order of thrusting in the foreland-imbricating system and increase proportions of neoformed to detrital mica in the more metamorphosed hinterland and deeply buried portions of the nappe pile. Individual thrusts accommodated the majority of their displacement during their initial incorporation into the foreland-imbricating system, and some thrusts remained active or were reactivated down to 15 Ma.     

Barium anomaly preceding K/T boundary: possible causes and implications on end Cretaceous events of K/T sections in Cauvery basin (India), Israel, NE-Mexico and Guatemala

Maastrichtian–Danian strata of the Cauvery basin as well as selected sections of NE-Mexico, Guatemala and Israel record Ba anomalies, away from the Cretaceous/Tertiary boundary (KTB) in addition to common occurrences of geochemical and stable isotopic anomalies across the KTB. Ba anomalies were recorded in monotonous shallow marine sandstones of the Cauvery basin (south India) which contain minor amounts of Ba-orthoclase. Barium anomalies were observed also in shallow marine carbonates in sections of Israel, NE-Mexico and Guatemala. Calculation of excess Ba with reference to PAAS (Post-Archaen Average Australian Shale), comparison of coeval geochemical anomalies, depositional pattern and associated petrographic and mineralogical features of the Cauvery basin revealed that while a first Ba peak was related to detrital influx, the second Ba peak was coincident with sea level fall which in turn may have been influenced by emission of volatile hydrocarbons and resultant climatic changes. In view of intrinsic involvement of Ba in various geochemical processes and occurrence of Ba anomalies in K/T sites distributed around the world (NE-Mexico, Guatemala and Israel), it is suggested that probable causes of such widespread Ba-anomalies should be taken into consideration while analyzing end Cretaceous events. These observations support the views espoused by many workers who have stated that the K/T boundary was also accompanied by many non-catastrophic events that might have contributed to environmental stress on marine fauna, as a result of which selective multi-stage extinctions occurred.     

Deducing the source and composition of rare earth mineralising fluids in carbonatites: insights from isotopic (C,O, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) data from Kangankunde,Malawi

Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and ⁸⁷Sr/⁸⁶Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8–15 wt% REE₂O₃, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The ⁸⁷Sr/⁸⁶Sr values (0.70302–0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (δ¹⁸O + 3 to + 5‰_VSMOW and δ¹³C ? 3.5 to ? 3.2‰_VPDB). In contrast, dolomite in the same samples has similar δ¹³C values but much higher δ¹⁸O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar δ¹⁸O and ⁸⁷Sr/⁸⁶Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: δ¹⁸O + 7.7 to + 10.3‰ and δ¹³C ?5.2 to ?6.0‰; ⁸⁷Sr/⁸⁶Sr 0.70296–0.70298) is not directly linked with the REE mineralisation.     

<Superscript>10</Superscript>Be, <Superscript>18</Superscript>O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands,New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO₂) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and εHf ? 0 CHUR in detrital zircons, sourced from the volcanics. ¹⁰Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.     

New <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar laser single-grain ages of muscovites from mylonitic schists in the Rodna Mountains,Eastern Carpathians,Romania: correlations with microstructure

The Rodna Mountains afford the most internal structural window into the crystalline units of the Eastern Carpathians in Romania. The Rodna Mountains consist of Variscan metamorphic nappes that were restacked in the Alpine phase of Carpathian development forming the Subbucovinian and Infrabucovinian nappes. In order to evaluate age of deformation, ten samples were taken from the zone of greenschist facies mylonitic schist that marks the Alpine tectonic boundary between the Subbucovinian and Infrabucovinian nappes and ⁴⁰Ar/³⁹Ar laser single-grain ages determined for schistosity-forming muscovite. Microstructural assessment of quartz and muscovite distinguished two deformation events. Single-grain ages from the microstructurally most strongly reworked samples (four samples) give a tight clustering of ages at ca. 95 Ma. The least reworked schists have a broader clustering of ages spanning ca. 200–280 Ma with a late Permian peak and some samples showing outlier ages in the range 200–100 Ma. The relative development of the outliers, which correlates with evidence for increased microstructural reworking, is interpreted to mark progressive isotopic resetting. The ca. 95 Ma ages for the most reworked schists are estimates for the age of the Alpine nappe stacking. The ca. 200–280 Ma ages are similar to those of magmatism, metamorphism, and sedimentation thought to mark post-Variscan-pre-Alpine rifting and ocean basin formation in parts of the Alps and may be the thermal imprint of a related event in the Eastern Carpathians.     

Extreme <Superscript>15</Superscript>N Depletion in Seagrasses

Seagrass beds form an important part of the coastal ecosystem in many parts of the world but are very sensitive to anthropogenic nutrient increases. In the last decades, stable isotopes have been used as tracers of anthropogenic nutrient sources and to distinguish these impacts from natural environmental change, as well as in the identification of food sources in isotopic food web reconstruction. Thus, it is important to establish the extent of natural variations on the stable isotope composition of seagrass, validating their ability to act as both tracers of nutrients and food sources. Around the world, depending on the seagrass species and ecosystem, values of seagrass N normally vary from 0 to 8?‰ δ¹⁵N. In this study, highly unusual seagrass N isotope values were observed on the east coast of Qatar, with significant spatial variation over a scale of a few metres, and with δ¹⁵N values ranging from +2.95 to ?12.39?‰ within a single bay during March 2012. This pattern of variation was consistent over a period of a year although there was a seasonal effect on the seagrass δ¹⁵N values. Seagrass, water column and sediment nutrient profiles were not correlated with seagrass δ¹⁵N values and neither were longer-term indicators of nutrient limitation such as seagrass biomass and height. Sediment δ¹⁵N values were correlated with Halodule uninervis δ¹⁵N values and this, together with the small spatial scale of variation, suggest that localised sediment processes may be responsible for the extreme isotopic values. Consistent differences in sediment to plant ¹⁵N discrimination between seagrass species also suggest that species-specific nutrient uptake mechanisms contribute to the observed δ¹⁵N values. This study reports some of the most extreme, negative δ¹⁵N values ever noted for seagrass (as low as ?12.4?‰) and some of the most highly spatially variable (values varied over 15.4?‰ in a relatively small area of only 655 ha). These results are widely relevant, as they demonstrate the need for adequate spatial and temporal sampling when working with N stable isotopes to identify food sources in food web studies or as tracers of anthropogenic nutrients.     

Nd,Sr and Pb isotopic and REE geochemical study of some Miocene submarine hydrothermal deposits (Kuroko deposits) in Japan

Neodymium, Sr and Pb isotopic compositions, along with rare earth element (REE) concentrations were determined for twelve black ores and one yellow ore from twelve localities of the Kuroko deposits, Japan. The ores were generated by submarine hydrothermal activity during the Miocene age. Neodymium isotopic compositions of the ores (_Nd: –4.9 to +6.5) mostly overlap with spatially associated igneous rocks. On a Nd versus Sr isotopic correlation diagram, however, ⁸⁷Sr/⁸⁶Sr ratios are shifted from the associated igneous rocks towards the higher contemporaneous seawater ratio. REE patterns are highly variable, ranging from light REE enriched to depleted, and show no Ce anomalies, as would be expected if they were derived from seawater. These results suggest that the REEs contained in ores were mainly derived from the associated igneous rocks, but that the ore Sr is a mixture derived from both seawater and the igneous rocks. Most Pb isotopic compositions fall within the range defined by the associated igneous rocks (²⁰⁶Pb/²⁰⁴Pb=18.35–18.84, ²⁰⁷Pb/²⁰⁴Pb=15.59–15.97 and ²⁰⁸Pb/²⁰⁴Pb=38.53–39.90), although several samples have very radiogenic compositions that were most likely derived from basement rocks. Our new Pb isotopic results display greater variation, and have a larger range of more radiogenic compositions than has been noted previously for these ores. In addition, the black ore with the most radiogenic Pb isotopic composition also has the least radiogenic Nd isotopic composition. This suggests that at least some of the Pb contained in the ores was derived mainly from older basement rocks. The large positive Eu anomalies for some black ores are consistent with a high-temperature origin for the parental fluids, irrespective of the source rock. The single yellow ore examined, however, has a small negative Eu anomaly, which may indicate derivation from a lower temperature fluid. Previous studies suggested that the Kuroko ores were formed in the presence of organic materials in an anoxic basin. Combined Nd, Sr, Pb and Os isotopic and REE abundance data indicate that multiple sources were involved in the genesis of Kuroko ores.     

Anomalous unradiogenic 87Sr//86Sr ratios in ultrahigh‐pressure crustal carbonates – evidence for fluid infiltration during deep subduction?

Marbles from Changpu (Dabie Shan, eastern China), subducted to 4.4 GPa, have ⁸⁷Sr/⁸⁶Sr values < 0.7040. These low ⁸⁷Sr/⁸⁶Sr values, which would imply a sedimentation age > 2 Ga if considered as primary signature, reflect fluid–rock interaction with a fluid from a low‐⁸⁷Sr/⁸⁶Sr source. The introduction of low‐⁸⁷Sr/⁸⁶Sr was paralleled by introduction of Mg and loss of Si, K and Na in such a way that carbonates from the purest marbles have the least evolved Sr isotopic composition. Introduction of Mg is also indicated by the distribution of calcite and dolomite. Calcite forms inclusions in garnet, whereas dolomite is restricted to the matrix. These chemical changes, inferred from the mineralogy, in combination with textural evidence require a mobile metamorphic fluid. P–T–X constraints for fluid generation and for permeability increase related to mineral reactions and phase transitions suggest that the marbles acquired their anomalous Sr‐isotopic composition during subduction below 60 km. The marbles with the least radiogenic Sr isotopic composition demonstrate that crustal rocks may lose their isotopic fingerprint during deep subduction.     

Isotopic composition (H,O, Cl,Sr) of ground brines of the Siberian Platform

New data on the geochemistry and isotopic composition of chloride brines of the Siberian Platform are presented. The distribution of stable isotopes (²H, ¹⁸O, and ³⁷Cl) in brines of the Tunguska, Angara-Lena, western part of the Yakutian and Olenek artesian basins and ⁸⁷Sr/⁸⁶Sr in brines of the western part of the Olenek artesian basin was studied in the context of the problem of genesis of highly mineralized groundwaters. Results of the study and comparative analysis of the geochemical and isotopic peculiarities of the Siberian Platform brines conform to the theory of brine formation through the interaction of connate waters with enclosing rocks.     

Sr and Sr/Sr in the Yamuna River System in the Himalaya: sources, fluxes, and controls on sr isotope composition

Sr and ⁸⁷Sr/⁸⁶Sr have been measured in the Yamuna river headwaters and many of its tributaries (YRS) in the Himalaya. These results, with those available for major ions in YRS rivers and in various lithologies of their basin, have been used to determine their contributions to riverine Sr and its isotopic budget. Sr in the YRS ranges from 120 to 13,400 nM, and ⁸⁷Sr/⁸⁶Sr from 0.7142 to 0.7932. Streams in the upper reaches, draining predominantly silicates, have low Sr and high ⁸⁷Sr/⁸⁶Sr whereas those draining the lower reaches exhibit the opposite resulting from differences in drainage lithology. ⁸⁷Sr/⁸⁶Sr shows significant co-variation with SiO₂/TDS and (Na^* + K)/TZ⁺ (indices of silicate weathering) in YRS waters, suggesting the dominant role of silicate weathering in contributing to high radiogenic Sr. This is also consistent with the observation that streams draining largely silicate terrains have the highest ⁸⁷Sr/⁸⁶Sr, analogous to that reported for the Ganga headwaters. Evaluation of the significance of other sources such as calc-silicates and trace calcites in regulating Sr budget of these rivers and their high ⁸⁷Sr/⁸⁶Sr needs detailed work on their Sr and ⁸⁷Sr/⁸⁶Sr. Preliminary calculations, however, indicate that they can be a significant source to some of the rivers.It is estimated that on an average, ∼25% of Sr in the YRS is derived from silicate weathering. In the lower reaches, the streams receive ∼15% of their Sr from carbonate weathering whereas in the upper reaches, calc-silicates can contribute significantly (∼50%) to the Sr budget of rivers. These calculations reveal the need for additional sources for rivers in the lower reaches to balance their Sr budget. Evaporites and phosphorites are potential candidates as judged from their occurrence in the drainage basin. In general, Precambrian carbonates, evaporites, and phosphorites “dilute” the high ⁸⁷Sr/⁸⁶Sr supplied by silicates, thus making Sr isotope distribution in YRS an overall two end member mixing. Major constraints in quantifying contributions of Sr and ⁸⁷Sr/⁸⁶Sr from different sources to YRS rivers are the wide range in Sr and ⁸⁷Sr/⁸⁶Sr of major lithologies, limited data on Sr and ⁸⁷Sr/⁸⁶Sr in minor phases and on the behavior of Sr, Na, and Ca during weathering and transport.The Ganga and the Yamuna together transport ∼0.1% of the global Sr flux at the foothills of the Himalaya which is in the same proportion as their contribution to global water discharge. Dissolved Sr flux from the Yamuna and its mobilization rate in the YRS basin is higher than those in the Ganga basin in the Himalaya, a result consistent with higher physical and chemical erosion rates in the YRS.     

Differential behavior of components of the <Superscript>238</Superscript>U-<Superscript>206</Superscript>Pb and <Superscript>235</Superscript>U-<Superscript>207</Superscript>Pb isotopic systems in polymineralic U ores

U-Pb systems were examined in samples (ranging from 4 to 10 cm³ in volume) of ore material taken from along a 3.5-m profile across a zone of U mineralization exposed in an underground mine at the Strel’tsovskoe U deposit in eastern Transbaikalia. The behaviors of two isotopic U-Pb systems (²³⁸U-²⁰⁶Pb and ²³⁵U-²⁰⁷Pb) are principally different in all samples from our profile. While the individual samples are characterized by a vast scatter of their T(²⁰⁶Pb/²³⁸U) age values (from 112 to 717 Ma), the corresponding T(²⁰⁷Pb/²³⁵U) values vary much less significantly (from 127 to 142 Ma) and are generally close to the true age of the U mineralization. The main reason for the distortion of the U-Pb system is the long-lasting (for tens of million years) migration of intermediate decay products in the ²³⁸U-²⁰⁶Pb(RD²³⁸U) in the samples. This process resulted in the loss of RD²³⁸U from domains with high U concentrations and the subsequent accommodation of RD²³⁸U at sites with low U concentrations. The long-term effect of these opposite processes resulted in a deficit or excess of ²⁰⁶Pb as the final product of ²³⁸U decay. The loss or migration of RD²³⁸U are explained by the occurrence of pitchblende in association with U oxides that have higher Si and OH concentrations than those in the pitchblende and a higher ⁺⁶U/⁺⁴U ratio. The finely dispersed character of the mineralization and the loose or metamict texture of the material are the principal prerequisites for RD²³⁸U loss and an excess of ²⁰⁶Pb in adjacent domains with low U concentrations. Domains with low U contents in the zone with U mineralization serve as geochemical barriers (because of sulfides contained in them) at which long-lived RD²³⁸U(²²⁶Ra, ²¹⁰Po, ²¹⁰Bi, and ²¹⁰Pb) were accommodated and subsequently caused an excess of ²⁰⁶Pb. The ²³⁵U-²⁰⁷Pb system remained closed because of the much briefer lifetime of the ²³⁵U decay products. This may account for the significant discrepancies between the T(²⁰⁶Pb/²³⁸U) and T(²⁰⁷Pb/²³⁵U) age values. RD²³⁸U was most probably lost via the migration of radioisotopes at the middle part and end of the ²³⁸U family (starting with ²²⁶Ra). The heavy Th, Pa, and U radioisotopes (²³⁴Th, ²³⁴Pa, ²³⁴U, and ²³⁰Th) that occur closer to the beginning of ²³⁸U decay, before ²²⁶Ra, only relatively insignificantly participated in the process. Our results show that the loss and migration of RD²³⁸U are, under certain conditions, the main (or even the only) process responsible for the distortion of the U-Pb system.     

Interpreting high-pressure phengite <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar laserprobe ages: an example from Saih Hatat,NE Oman

New single grain fusion and core-rim ⁴⁰Ar/³⁹Ar laserprobe phengite data from the Saih Hatat high-pressure terrane in NE Oman show that individual samples yield a range of apparent ages which is similar to that previously reported from across the entire terrane. The majority of the determined ages are older than the previously reported U-Pb zircon peak metamorphic age. Core to rim age variations within individual grains range from no discernible difference across the grain to grains with older cores, or, rarely, older rims; some samples manifest all three patterns. Numerical diffusion modelling shows that due to the peak temperature of ca. 550°C, the measured apparent ages cannot be explained by simple cooling or by partial retention of crystallisation or detrital ages in an open system. The age variability is better explained by spatially and temporally variable open or closed system behaviour at the mm-cm scale coupled with pervasive and heterogeneously distributed excess argon. Anomalously old eclogite phengite ⁴⁰Ar/³⁹Ar ages are due either to internally derived ⁴⁰Ar inherited from a K-bearing precursor, or externally derived ⁴⁰Ar distributed by grain boundary fluids. Mica-rich schists within the eclogite boudins yield younger phengite ages, suggesting excess argon was absent or diluted. Pelites hosting the eclogite appear to have been affected by later fluid ingress during deformation and greenschist-facies overprint and yield very variable ages commonly with apparently older rims on younger cores. The grain- and sample-scale age variations measured in Saih Hatat indicate that the grain boundary network in eclogite pods was not an efficient transfer pathway for argon transport, whereas the grain boundary network in the surrounding pelites acted as a more efficient pathway on the timescale of the metamorphic cycle.     

In situ Sr/Sr investigation of igneous apatites and carbonates using laser-ablation MC-ICP-MS

In situ Sr isotopic compositions of coexisting apatite and carbonate for carbonatites from the Sarfartoq alkaline complex, Greenland, have been determined by laser-ablation multicollector inductively coupled plasma mass spectrometry. This study is the first to examine the extent of Sr isotopic homogeneity among coexisting igneous minerals containing high Sr (>3000 ppm) and low Rb (?1 ppm) contents within a single ∼50-μm-thick thin-section mount. This technique is capable of producing measured ⁸⁷Sr/⁸⁶Sr values with analytical precision (∼0.005%, 2σ) approaching those obtained by thermal ionization mass spectrometry but in a much shorter interval of time (100 s vs. >1 h, respectively). The combined total analyses (n = 107) of apatite and carbonate yield ⁸⁷Sr/⁸⁶Sr compositions ranging from ∼0.7025 to ∼0.7031. This relatively large variation in Sr isotopic compositions (∼0.0006) is ∼1 order of magnitude larger than the estimated external reproducibility (∼0.00005, 2σ) of the method. The large range in ⁸⁷Sr/⁸⁶Sr values suggests that apatite and carbonate precipitated predominantly under nonequilibrium conditions. The isotopic variations observed within individual hand specimens may therefore reflect larger (regional) scale open-system processes, possibly involving mixing of carbonatitic melts derived from distinct mantle sources or from a common isotopically heterogeneous mantle.     

Detection of <Superscript>3</Superscript>H and <Superscript>85</Superscript>Kr in groundwater from arsenic-bearing crystalline bedrock of the Goose River basin,Maine

Presence of young groundwater (post-1950) in the Goose River basin is demonstrated with ³H and ⁸⁵Kr analyses. A total of 96 wells and four springs were sampled quarterly from 1999 to 2001 to determine the extent of any recent recharge and to what depth hydraulic continuity existed in the groundwatershed (33.3 km²). Recharge groundwater is less than 50 years in about 31% (³H) to 37% (⁸⁵Kr) of sampled wells and 75% of sampled springs. Young groundwater ages are recorded in wells up to 320 m in depth within fractured- and arsenic-bearing crystalline bedrock. Total arsenic 10 g L^–1 occurs significantly in drinking water with young groundwater flowing through the pumping well intervals. As_total occurs in 89% (⁸⁵Kr) to 93% (³H) of all wells with post-1950 groundwater ages. Young groundwater recharge and elevated geogenic arsenic were discovered only in the anatectic granitoids and migmatized country rock of the southwestern part of the Goose River basin.     

The dynamics of central Main Ethiopian Rift waters: Evidence from δD, δO and Sr/Sr ratios

Water samples from cold and geothermal boreholes, hot springs, lakes and rivers were analyzed for δD, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr compositions in order to investigate lake water–groundwater mixing processes, water–rock interactions, and to evaluate groundwater flow paths in the central Main Ethiopian Rift (MER) of the Ziway–Shala basin. Different ranges of isotopic values were recorded for different water types: hot springs show δ¹⁸O −3.36 to +3.69 and δD −15.85 to +24.23, deep Aluto-Langano geothermal wells show δ¹⁸O −4.65 to −1.24 and δD −12.39 to −9.31, groundwater wells show δ¹⁸O −3.99 to +5.14 and δD −19.69 to +32.27, whereas the lakes show δ¹⁸O and δD in the range +3.98 to +7.92 and +26.19 to +45.71, respectively. The intersection of the Local Meteoric Water Line (LMWL: δD = 7 δ¹⁸O + 11.2, R² = 0.94, n = 42) and the Local Evaporation Line (LEL: δD = 5.63δ¹⁸O + 8, n = 14, R² = 0.82) was used to estimate the average isotopic composition of recharge water into the basin (δD = −5.15 and δ¹⁸O = −2.34). These values are depleted if compared with the modern-day average precipitation, presumably indicating paleo-groundwater components recharged during previous humid climatic phases. The measured stable isotope values indicate that the geothermal wells, some of the hot springs and groundwater wells mainly consist of meteoric water. The Sr isotopic signatures in all waters are within the range of the Sr isotopic composition of the rift basalts and rhyolites. The variability of Sr isotopic data also pinpoints complex water–rock interaction and mixing processes in groundwater and surface water. The ⁸⁷Sr/⁸⁶Sr ratio ranges from 0.70445 to 0.70756 in the hot springs, from 0.70426 to 0.70537 in two deep geothermal wells, and from 0.70673 to 0.70721 in the rift lakes Ziway, Langano, Shala and Awasa. The radiogenic composition recorded by the lakes indicates that the input water was predominantly affected by progressive interaction with rhyolitic volcanics and lacustrine sediments.     

Relationship between electrical conductivity, <Superscript>18</Superscript>O of water and NO<Subscript>3</Subscript> content in different streamflow stages

The Ballenera Creek has 160 km² being a small catchment in the Pampa Plain in Argentina. This area has been deeply modified by human action through agricultural activities. From 2013 to 2017, electrical conductivity, stable isotopes of water and nitrate concentration monitoring program were conducted. The sampling included weekly and bimonthly samples in two sites along the stream, several groundwater wells and monthly precipitation. Chemical and isotopic tracers are used to discriminate the streamflow components and to evaluate their incidence in the nitrate concentration. The easiest conceptual model for gaining streams contemplates two main elements: direct runoff and groundwater (baseflow and pre-event water). The direct runoff has the lowest electrical conductivity and ¹⁸O_w variable content. The baseflow component is characterized by the highest electrical conductivity and isotope composition quite constant. Finally, pre-event water has an intermediate electrical conductivity and isotopic content close to the rainfall-weighted average composition. The nitrate concentration obtained was in general related to the different stream stages and was a useful indicator to evaluate the fertilization in agricultural zones.     

Tracing the exhumation of the Eclogite Zone (Tauern Window,Eastern Alps) by <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating of white mica in eclogites

New radiometric ages from the Subpenninic nappes (Eclogite Zone and Rote Wand – Modereck Nappe, Tauern Window) show that phengites formed under eclogite-facies metamorphic conditions retain their initial isotopic signature, even when associated lithologies were overprinted by greenschist- to amphibolite-facies metamorphism. Different stages of the eclogite-facies evolution can be dated provided ⁴⁰Ar/³⁹Ar dating is combined with micro-structural analyses. An age of 39 Ma from the Rote Wand – Modereck Nappe is interpreted to be close to the burial age of this unit. Eclogite deformation within the Eclogite Zone started at the pressure peak along distinct shear zones, and prevailed along the exhumation path. An age of ca. 38 Ma is only observed for eclogites not affected by subsequent deformation and is interpreted as maximum age due to the possible influence of homogenously distributed excess argon. During exhumation deformation was localised along distinct mylonitic shear zones. This stage is mainly characterised by the formation of dynamically recrystallized omphacite2 and phengite. Deformation resulted in the resetting of the Ar isotopic system within the recrystallized white mica. Flat argon release spectra showing ages of 32 Ma within mylonites record the timing of cooling along the exhumation path, and the emplacement onto the Venediger Nappe. Ar-release patterns and ³⁶Ar/⁴⁰Ar vs.³⁹Ar/⁴⁰Ar isotope correlation analyses indicate no significant ⁴⁰Ar-loss after initial closure, and only a negligible incorporation of excess argon. From the pressure peak onwards, eclogitic conditions prevailed for almost 8–10 Ma.     

Rb–Sr and Sm–Nd isotopic systematics of the Hayachine–Miyamori ophiolitic complex: Melt generation process in the mantle wedge beneath an Ordovician island arc

The Hayachine–Miyamori (HM) ophiolitic complex in the Kitakami Mountains, northeastern Japan consists of ultramafic tectonite and cumulate members. The most fertile lherzolites have mineral and trace element compositions similar to those of abyssal peridotites. They show 350–430 Ma Nd depleted mantle model ages, which are within the range of the K–Ar emplacement ages obtained from intrusive gabbroic rocks, suggesting a partial melting event just before the emplacement. The measured ¹⁴³Nd/¹⁴⁴Nd ratio of clinopyroxene in the tectonite peridotites shows positive correlation with ¹⁴⁷Sm/¹⁴⁴Nd and decreases with increasing refractoriness, which cannot be explained by a simple melting and melt extraction to a various extent followed by radiogenic ingrowth. It clearly suggests influx of a melt/fluid enriched in highly incompatible trace elements during melting. Time corrected isotopic compositions of the HM complex exhibit a clear island arc signature with uniform initial isotopic ratio (⁸⁷Sr/⁸⁶Sr = 0.7035–0.7041, ε_Nd = + 7.8–+ 5.0). Application of an open-system melting model to the observed trace element abundances in clinopyroxene suggests influx of three distinct agents to the HM mantle with the following characteristics: (1) moderate enrichment in highly incompatible elements with negative anomalies of Sr and Zr; (2) extensive enrichment of highly incompatible elements with positive Sr and negative Zr anomalies; and (3) extensive enrichment of highly incompatible elements with positive anomalies of Sr and Zr. These characteristics cover a variety of slab-derived components proposed in the literatures, suggesting the agents responsible for the open-system melting in the HM ophiolite might represent full spectrum of slab-derived components from back-arc to fore-arc regions of the Ordovician island arc system.     

Accurate Determination of Sr Isotopic Compositions in Clinopyroxene and Silicate Glasses by LA‐MC‐ICP‐MS

The low‐Sr content (generally < 100 μg g^?1) in clinopyroxene from peridotite makes accurate Sr isotopic determination by LA‐MC‐ICP‐MS a challenge. The effects of adding N₂ to the sample gas and using a guard electrode (GE) on instrumental sensitivity for Sr isotopic determination by LA‐MC‐ICP‐MS were investigated. Results revealed no significant sensitivity enhancement of Sr by adding N₂ to the ICP. Although using a GE led to a two‐fold sensitivity enhancement, it significantly increased the yield of polyatomic ion interferences of Ca‐related ions and TiAr⁺ on Sr isotopes. Applying the method established in this work, ⁸⁷Sr/⁸⁶Sr ratios (Rb/Sr < 0.14) of natural clinopyroxene from mantle and silicate glasses were accurately measured with similar measurement repeatability (0.0009–0.00006, 2SE) to previous studies but using a smaller spot size of 120 μm and low‐to‐moderate Sr content (30–518 μg g^?1). The measurement reproducibility was 0.0004 (2s, n = 33) for a sample with 100 μg g^?1 Sr. Destruction of the crystal structure by sample fusion showed no effect on Sr isotopic determination. Synthesised glasses with major element compositions similar to natural clinopyroxene have the potential to be adopted as reference materials for Sr isotopic determination by LA‐MC‐ICP‐MS.