Lithium enrichment and isotopic variation in minerals from peridotite xenoliths from northwestern Ethiopian plateau

We report Lithium (Li) concentrations and isotopic compositions for co-existing olivine, orthopyroxene (opx), and clinopyroxene (cpx) mineral separates from depleted and metasomatised peridotite xenoliths hosted by basaltic lavas from northwestern Ethiopian plateau (Gundeweyn area). The peridotites contain five lherzolites and one harzburgite and are variably depleted and enriched in LREE relative to HREE. In both depleted and enriched lherzolites, Li is preferentially incorporated into olivine (2.4-3.3 ppm) compared to opx (1.4-2.1 ppm) and cpx (1.4-2.0 ppm) whereas the Li contents of olivines (5.4 ppm) from an enriched harzburgiteare higher than those of lherzolites. Olivines from the samples show higher Li abundances than normal mantle olivines (1.6-1.9 ppm) indicating the occurrence of Li enrichments through melt-preroditite interaction. The average δ⁷ Li values range from +2.2 to +6.0‰ in olivine, from -0.1 to +2.0‰ in opx and from -4.4 to -0.9‰ in cpx from the lherzolites. The Li isotopic composition (3.5‰) of olivines from harzburgite fall within the range of olivine from lherzolites but the opxs show low in δ⁷Li (-2.0‰). Overall Li isotopic compositions of olivines from the peridotites fall within the range of normal mantle olivine, δ⁷Li values of ~+4±2‰ within uncertainty, reflecting metasomatism (enrichment) of the peridotites by isotopically heavy Li-rich asthenospheric melt. Li isotope zonation is also observed in most peridotite minerals. Majority of olivine grains display isotopically heavy cores and light rims and the reverse case is observed for some olivine grains. Orthopyroxene and clinopyroxene grains show irregular distribution in δ⁷Li. These features of Li isotopic compositions within and between grains in the samples reflect the effect of diffusion-driven isotopic fractionation during meltperidotite interaction and cooling processes.     

Lithium isotopic composition of Central American Volcanic Arc lavas: implications for modification of subarc mantle by slab-derived fluids

Li contents and isotopic compositions were determined for a suite of well-characterized basaltic lavas from the Central American Volcanic Arc (CAVA). Variable Li/Y (0.2–0.5), Li/Sc (0.1–0.4), and δ⁶Li values (+2.6 to −7.7‰) attest to significant compositional heterogeneity in the subarc mantle. Within specific arc segments, these parameters correlate strongly with each other and with a number of other constituents (e.g., K, Rb, Ba, B/La, ¹⁰Be/⁹Be, ⁸⁷Sr/⁸⁶Sr, U/Ce, and ²³⁰Th/²³²Th, among others); these correlations are particularly strong for Nicaragua samples. Coupling of this particular set of constituents is best explained in terms of addition of ‘subduction components' to the subarc mantle. Moreover, their selective enrichment with respect to relatively fluid-immobile incompatible elements signifies the dominance of fluid vs. silicate melt transport of slab components to the subarc mantle. Several interesting nuances are revealed by the Li data. First, although Li and B are strongly correlated in both Costa Rica and Nicaragua, there are systematic along-strike variations in Li/B that are consistent with these elements having different ‘fluid release patterns' from subducted slab segments. For example, Li/B is highest in Costa Rica where auxiliary evidence indicates higher subduction zone temperatures; apparently B is preferentially depleted and Li retained in the slab under warmer conditions. The same relations are reflected in Li/¹⁰Be and other subduction tracer systematics, all of which point to larger subduction contributions below Nicaragua. Yet, even Nicaragua lavas vary widely in levels of subduction enrichment. High-Ti basalts from Nejapa are the least enriched and have the highest δ⁶Li (1.4 to 2.6‰); these values are greater than in fresh MORB (ca. −4‰) and are not easily explained by additions of subducted Li because most oceanic crustal rocks and marine sediments have lower δ⁶Li than MORB (with typical values between −8 and −20‰). Thus, it appears the Nejapa data may be representative of isotopically light mantle domains. Relatively light δ⁶Li values in an undepleted spinel lherzolite (+11.3‰) from Zabargad Is. (Red Sea) and in primitive backarc basalts (−1.6 to −0.5‰) from Lau Basin support this conclusion. Considering representative fluid and mantle endmember compositions, the CAVA data are consistent with limited (up to a few percent) additions of slab-derived fluids to a heterogeneous mantle containing variably depleted and enriched domains to form the respective magma sources. In our view, the subarc mantle is heterogeneous on a small scale, but some arc sectors clearly received greater slab inputs than others.     

Lithium isotopic evidence for subduction of the Indian lower crust beneath southern Tibet

Post-collisional K-rich volcanic rocks (KVRs) can provide an opportunity to constrain the architecture of the lithosphere and the mechanisms of plateau uplift. However, their petrogenesis and geodynamic setting remain in dispute. Lithium concentrations and isotopic compositions of 87 potassic, ultrapotassic and Mg-rich potassic volcanic rocks (PVRs, UPVs, and MPRs, respectively) in SW Tibet, along with new Pb–Sr–Nd isotope data and whole-rock analyses, are used to constrain their mantle source and genesis. These rocks are characterized by very similar δ⁷Li values: PVRs vary from −4.9‰ to +3.2‰, UPVs from −3.9‰ to +1.7‰, and MPRs from −1.2‰ to +3.5‰. They can be classified into two groups: Group I (19 out of 87 samples) with heavier δ⁷Li values (+1.0‰ to +3.5‰) similar to those reported for mid-ocean-ridge and ocean-island basalts (MORBs and OIBs, respectively), and Group II (68 out of 87 samples) with lighter values (−4.9‰ to +1.0‰) similar to those of Indian lower crust. These variable isotopic compositions may record the isotopic signature of the early-middle Miocene subcontinental lithospheric mantle (SCLM). This paper demonstrates the existence of isotopically light mantle domains beneath the Lhasa terrane, which were ascribed to the interaction with fluids/melts derived from the subducted Indian lower crust. The modeling curves of Indian lower crust with a metasomatized mantle composition fully account for compositional variations in the PVRs, UPVs, and MPRs. They were generated by the partial melting of SCLM, which was metasomatized by fluids/melts derived from the subducted Indian lower crust (ca. 4–14%, ca. 4–10%, and ca. 6–10% for the PVRs, UPVs, and MPRs, respectively). The Li isotopic data indicate that the Indian lower crust was subducted beneath the central Lhasa subterrane, and this sheds new light on the formation of the Tibet Plateau.     

Boron and lithium isotopes as groundwater tracers: a study at the Fresh Kills Landfill,Staten Island,New York,USA

A study was conducted at the Fresh Kills landfill, Staten Island, New York to investigate the use of B and Li isotopes as tracers of mixing and flow in the groundwater environment. Four end-member waters are present at the Fresh Kills: freshwater, seawater, a geochemically distinct transitional groundwater (that occurs in the zone of mixing between seawater and freshwater) and landfill leachate. The δ¹¹B and δ⁶Li values of end-member waters are distinct and have isotopic compositions that reflect the solute sources: freshwater δ¹¹B∼+30‰, δ⁶Li∼−22‰; transition zone groundwaters δ¹¹B∼+20‰, δ⁶Li∼−27‰; seawater δ¹¹B+40 to +75‰, δ⁶Li−37 to−44‰; leachate δ¹¹B∼+10‰ (δ⁶Li not determined). Those wells influenced by seawater exhibited a clear chemical mixing trend, with seawater contributions ranging from 3 to 85%. Well waters with a high percentage of seawater (>30%) had δ¹¹B values that were within 1‰ of the seawater value (+40‰), whereas a trend of increasing δ¹¹B values (+55 to +75‰) was observed for wells with a lower percentage of seawater (<30%). δ⁶Li values for well waters impacted by mixing with seawater ranged from−37 to−44‰, significantly more negative than pure seawater (−31‰). This deviation from the isotopic composition of seawater, for both δ¹¹B and δ⁶Li values, represents non-conservative behavior and is likely the result of isotopic fractionation during ion exchange reactions. The wide range of δ¹¹B and δ⁶Li values and the distinct isotopic compositions of end-member waters makes B and Li isotopes useful for recognizing solute sources, however isotopic fractionation may limit their use as simple tracers of groundwater flow and mixing.     

Lithium elemental and isotopic disequilibrium in minerals from peridotite xenoliths from Shangzhi,NE China: products of recent melt/fluid-peridotite interaction

Lithium elemental and isotopic disequilibrium has frequently been observed in the continental and oceanic mantle xenoliths, but its origin remains controversial. Here, we present a combined elemental and Li isotopic study on variably metasomatised peridotite xenoliths entrained in the Cenozoic basalts from Shangzhi in Northeast (NE) China that provides insight into this issue. Li concentration (0.3–2.7 ppm) and δ⁷Li (mostly 2‰–6‰) in olivine from the Shangzhi peridotites are similar to the normal mantle values and show roughly negative correlations with the indices of melt extraction (such as modal olivine and whole rock MgO). These features are consistent with variable degrees of partial melting. In contrast, clinopyroxene from the Shangzhi xenoliths shows significant Li enrichment (0.9–6.1 ppm) and anomalously light δ⁷Li (??13.8‰ to 7.7‰) relative to normal mantle values. Such features can be explained by Li diffusion from silicate melts or Li-rich fluids occurring over a very short time (several minutes to several hours). Moreover, the light Li isotopic compositions preserved in some bulk samples also indicate that these percolated melts/fluids have not had enough time to isotopically equilibrate with the bulk peridotite. We thus emphasize that Li isotopic fractionation in the Shangzhi mantle xenoliths is mainly related to Li diffusion from silicate melts or Li-rich fluids that took place shortly before or coincident with their entrainment into the host magmas.     

Evidence for microbial activity in British and Irish Ordovician pillow lavas

Pyrite is consistently found in modern seafloor vesicular basalts and has a sulphur isotopic composition consistent with microbial activity. We present S isotope data from pyrite in Ordovician pillow lavas at localities across the British Isles, which yield a range of δ³⁴S compositions consistent with two components of sulphur: groundmass pyrite (~0 ± 4‰) and ³²S‐enriched pyrite in the vesicles (−8‰ to −27‰). The latter are recorded from vesicular lavas in four different terranes, representing different settings at the margins of the Iapetus Ocean. Whereas a component of magmatic sulphate is recognized in the groundmass values, the isotopically light data in the vesicles are consistent with microbial reduction of seawater sulphate in sub‐seafloor lavas. This is consistent with modern examples and indicates considerable longevity for this sub‐seafloor microbial habitat. Copyright © 2014 John Wiley & Sons, Ltd.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.     

Hydrothermal flow systems in the Midcontinent Rift: oxygen and hydrogen isotopic studies of the North Shore Volcanic Group and related hypabyssal sills,Minnesota

Rift-related lavas of the North Shore Volcanic Group (NSVG) are intruded by plutonic rocks of the Duluth Complex along the unconformity between the NSVG and the underlying Proterozoic metasedimentary rocks (Animikie Group) and Archean volcano-sedimentary and plutonic rocks. Heat associated with the emplacement of the mafic intrusions generated fluid flow in the overlying plateau lavas. δ¹⁸O values for whole rocks from the NSVG and hypabyssal sills range from 5.5 to 17.7‰ and 5.3 to 11.5‰, respectively, and most values are higher than those considered “normal” for basaltic rocks (5.4 to 6.0‰). In general, there is a positive correlation between whole rock δ¹⁸O and water content, which suggests that elevated δ¹⁸O values are related primarily to secondary mineral growth and isotopic exchange during hydrothermal alteration and metamorphism. δ¹⁸O_H2O values computed from amygdule-filling minerals such as smectite, chlorite, and epidote found in low- to high-temperature metamorphic zones range from ∼−1 to 6‰ with an average value of ∼3‰. Smectite in the lower-grade zones gives computed δD_H2O values between −26 and −83‰, whereas epidote in the higher-grade zones gives δD_H2O values of −15 to 6‰. Fluid isotopic compositions computed from epidote and smectite values are suggestive of the involvement of at least two fluids during the early stages of amygdule filling. Fluid δD and δ¹⁸O values determined from epidote at the higher metamorphic grades indicate that seawater dominated the deeper portions of the system where greenschist facies assemblages and elevated δ¹⁸O values were produced in flow interiors, as well as margins. Smectite isotopic compositions suggest that meteoric water was predominant in the shallower portions of the system. The increase in δ¹⁸O values of massive flow interiors with depth is interpreted as a result of rock interaction with a fluid of constant oxygen isotopic composition with increasing temperature. The stable isotopic data are supportive of previous suggestions that seawater was involved in the hydrothermal system associated with the Midcontinent Rift. Although the origin of the seawater remains problematic, it appears that marine incursions may have occurred during the late stages of Portage Lake volcanism, and periodically thereafter.     

The application of C isotope measurements to the identification of the sources of C in diamonds: a review

In the past decade, the isotopic compositions of C in > 600 inclusion-bearing diamonds have been determined. Such analyses have revealed the following isotopic characteristics: (1) peridotitic diamonds, which typically contain garnet, chromite, olivine and/or orthopyroxene inclusions with refractory compositions (high Mg, Cr), have δ¹³C values predominantly between −10 and −1‰, with a sharp peak in the distribution near −5‰; (2) eclogitic diamonds, which commonly contain inclusions of omphacitic clinopyroxene, Cr-poor pyrope, and/or eclogitic accessory minerals such as rutile, kyanite, coesite or sanidine, have δ¹³C values between −34 and +3‰, with a smaller peak near −5‰; (3) the isotopic compositions obtained for suites of diamonds from individual occurrences are, in general, unique and do not resemble the range and distribution obtained by amalgamating the diamond isotope data from a number of localities; (4) isotopic zoning patterns and heterogeneities are found in some diamonds; cores of coated diamonds tend to be depleted in¹³C relative to the rims, and within single octahedral diamonds δ¹³C variations of nearly 6‰ have been reported.Because expected C isotope fractionations at mantle temperatures are small, attempts to model the full range of diamond isotope values through fractionating a homogeneous mantle C source have been unsuccessful. Nevertheless, fractionation is probably responsible for some of the observed variation in δ¹³C values. Two other models have also been proposed to account for the diamond characteristics outlined above. The “primordial model” suggests that the range and distribution of C isotope compositions are inherited from primordial C in the mantle which has an inhomogeneous isotopic composition, such as that found in meteorites. The “subduction model” suggests that subducted, crustal C is the source of C in diamonds, as organic and inorganic C compounds in the crust exhibit a range of δ¹³C values similar to that observed in diamonds. This paper reviews the C isotope characteristics of diamonds and compares the models which have been proposed to explain the origins of these characteristics.     

Geology and Isotope Geochemistry of the Dongzhongla Pb–Zn Deposit in Tibet: Implications for the Origin of the Ore‐Forming Fluids and Storage Condition of Certain Metals

As a newly discovered medium‐sized deposit (proven Pb + Zn resources of 0.23 Mt, 9.43% Pb and 8.73% Zn), the Dongzhongla skarn Pb–Zn deposit is located in the northern margin of the eastern Gangdese, central Lhasa block. Based on the geological conditions in this deposit of ore‐forming fluids, H, O, C, S, Pb, Sr, and noble gas isotopic compositions were analyzed. Results show that δ¹⁸O_SMOW of quartz and calcite ranged from −9.85 to 4.17‰, and δD_SMOW ranged from −124.7 to −99.6‰ (where SMOW is the standard mean ocean water), indicating magma fluids mixed with meteoric water in ore‐forming fluids. The δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from −1.4 to −1.1‰ and from 5.3 to 15.90‰, respectively, show compositions consistent with the carbonate limestone in the surrounding rocks, implying that the carbon was primarily sourced from the dissolution of carbonate strata in the Luobadui Formation. The ore δ³⁴S composition varied in a narrow range of 2.8 to 5.7‰, mostly between 4‰ and 5‰. The total sulfur isotopic value δ³⁴S was 4.7‰ with characteristics of magmatic sulfur. The ³He/⁴He values of pyrite and galena ranged from 0.101 to 5.7 Ra, lower than those of mantle‐derived fluids (6 ± 1 Ra), but higher than those of the crust (0.01–0.05 Ra), and therefore classified as a crust–mantle mixed source. The Pb isotopic composition for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of the ores were in the ranges of 18.628–18.746, 15.698–15.802, and 39.077–39.430, respectively, consistent with the Pb isotopic composition of magmatic rocks in the deposit, classified as upper‐crust lead. The ore lead was likely sourced partially from the crustal basement of the Lhasa Terrane. The initial (⁸⁷Sr/⁸⁶Sr)_i value from five sulfide samples ranged from 0.71732 to 0.72767, and associated ore‐forming fluids were mainly sourced from the partial melting of the upper‐crust materials. Pb isotopic compositions of ore sulfides from the Dongzhongla deposit are similar to that of the Yuiguila and Mengya'a deposit, indicating that they have similar sources of metal‐rich ore‐forming solution. According to basic skarn mineralogy, the economic metals, and the origin of the ore‐forming fluids, the Dongzhongla deposit was classified as a skarn‐type Pb–Zn deposit.     

Hydrogen and oxygen isotopic compositions of sedimentary kaolin deposits,Egypt: Paleoclimatic implications

The clay fractions of sedimentary kaolin deposits representing different ages (Carboniferous and Cretaceous), types (pisolitic flint and plastic), and localities (Sinai and Aswan) from Egypt were analyzed for their H and O isotopic compositions to examine the paleoclimate conditions during their formation. The δD values of the Carboniferous deposits in Sinai range between −67‰ and −88‰, while the values for the Cretaceous deposits in Sinai range between −59‰ and −75‰. The δ¹⁸O values of the Carboniferous deposits range from 17.9‰ to 19.4‰ and the values for the Cretaceous deposits range between 19.2‰ and 20.4‰. The relatively low δD and δ¹⁸O values of the Carboniferous deposit at the Abu Natash area (−67‰ and 17.9‰, respectively) compared to other Carboniferous deposits (averages of −83.3‰, and 18.8‰ for δD and δ¹⁸O, respectively) could be due to isotopic exchange between this deposit and the adjacent dolomite and/or the enclosed hydrothermally-formed Mn ores of the Carboniferous Um Bogma Formation. The δD and δ¹⁸O values of the Cretaceous pisolitic flint kaolin deposit from Aswan (averages of −65‰ and 20.3‰, respectively) and plastic kaolin from the same area (averages of −66‰ and 19.5‰, respectively) are almost identical. The differences in the δ¹⁸O values between the clay fractions of the pisolitic flint kaolin (20.3‰) and the previously analyzed bulk kaolin of the same deposit (average of 17.5‰) suggest a significant effect of non-clay minerals on the isotopic compositions of the kaolin deposits.The H and O isotopic compositions plot close to the kaolinite line that marks the isotopic composition of kaolinite in equilibrium with meteoric water at 20 °C. This indicates that the kaolinite from both the Carboniferous and Cretaceous deposits in Egypt formed by meteoric water weathering of the source rock(s). The δD and δ¹⁸O values also suggest that kaolinite of these deposits formed under warm-temperate to tropical conditions. The slight deviations of some samples from the kaolinite line suggest post-depositional modifications of the isotopic compositions of studied deposits probably due to the interaction between earlier-formed kaolinite and downward percolating meteoric water.The δD and δ¹⁸O values of the Cretaceous and Carboniferous deposits from all localities suggest that both deposits formed under similar climatic conditions due to the location of Egypt at almost the same distance from the equator either to the south during the Carboniferous or to the north during the Cretaceous.     

Isotope systematics of Li, Sr, Nd, and volatiles in Indian Ocean MORBs of the Rodrigues Triple Junction: Constraints on the origin of the DUPAL anomaly

The DUPAL anomaly, a radiogenic isotope anomaly discovered in the Indian Ocean mantle, has been interpreted as due to a large-scale mantle heterogeneity. To provide new constraints on the DUPAL origin, we analyzed isotope ratios of Li, Sr, and Nd in fresh N-MORB glasses recovered from the Rodrigues Triple Junction in the Indian Ocean, and from the North Atlantic. The Li isotopic compositions of the Indian Ocean DUPAL N-MORBs were comparable to those of the North Atlantic non-DUPAL N-MORBs. The source of the DUPAL signature in Indian Ocean MORBs and the E-MORB-type enriched mantle source have quite different Li isotopic compositions. The ¹⁴³Nd/¹⁴⁴Nd values of both sources are significantly lower than those of the North Atlantic N-MORBs. The δ⁷Li values of most oceanic island basalts with similar low ¹⁴³Nd/¹⁴⁴Nd signatures are also higher than those of the North Atlantic N-MORBs, except for several Koolau lavas. The Li isotope results support the recent proposal that significant amounts of recycled lower continental crust might produce the radiogenic isotope signatures of the Indian Ocean DUPAL source.     

Two pulses of mineralization and genesis of the Zhaxikang Sb–Pb–Zn–Ag deposit in southern Tibet: Constraints from Fe–Zn isotopes

Zhaxikang is one large Sb–Pb–Zn–Ag deposit located in the North Himalaya of southern Tibet. To date, the genesis of this deposit still remains controversial. Here, we present new pyrite Fe and sphalerite Zn isotopic data for the first three stages of mineralization, Fe–Zn isotopic data for Mn–Fe carbonate that formed during the first two stages of mineralization, and Zn isotopic data for the slate wall rocks of the Jurassic Ridang Formation to discuss the genesis of the Zhaxikang deposit. The overall δ⁵⁶Fe and δ⁶⁶Zn values range from −0.80‰ to 0.43‰ and from −0.03‰ to 0.38‰, respectively. The δ⁵⁶Fe values of Mn–Fe carbonates are lighter than those of associated pyrite in six mineral pairs, indicating that the iron carbonates are preferentially enriched in light Fe isotopes relative to pyrite. The sphalerite has lighter δ⁶⁶Zn values than associated Mn–Fe carbonates in three mineral pairs.The δ⁵⁶Fe values of pyrite that formed during the first three stages of mineralization gradually increase from stage 1 (−0.33‰ to −0.09‰) through stage 2 (−0.30‰ to 0.19‰) to stage 3 (0.16‰–0.43‰). In comparison, the sphalerite that formed during these stages has δ⁶⁶Zn values that gradually decrease from stage 1 (0.16‰–0.35‰) through stage 2 (0.09‰–0.23‰) to stage 3 (−0.03‰ to 0.22‰). These data, in conjunction with the observations of hand specimens and thin sections, suggest that the deposit was overprinted by a second pulse of mineralization. This overprint would account for these Fe–Zn isotopic variations as well as the kinetic Rayleigh fractionation that occurred during mineralization. The temporally increasing δ⁵⁶Fe and decreasing δ⁶⁶Zn values recorded in the deposit are also coincident with an increase in alteration, again supporting the existence of two pulses of mineralization. The δ⁵⁶Fe values of the first pulse of ore-forming fluid were calculated using theoretical equations, yielding values of −0.54‰ to −0.34‰ that overlap with those of submarine hydrothermal solutions (−1‰ to 0‰). However, the δ⁵⁶Fe values of the stage 3 pyrite are heavier than those of typical submarine hydrothermal solutions, which suggests that the second pulse of mineralization was probably derived from a magmatic hydrothermal fluid. In addition, the second pulse of ore-forming fluid has brought some Fe and taken away parts of Zn, which results the lighter δ⁶⁶Zn values of sphalerite and heavier δ⁵⁶Fe values of pyrite from the second pulse of mineralization. Overall, the Zhaxikang deposit records two pulses of mineralization, and the overprint by the second pulse of mineralization causes the lighter δ⁶⁶Zn values and heavier δ⁵⁶Fe values of modified samples.     

Determining the origin of carbon dioxide and methane in the gaseous emissions of the San Vittorino plain (Central Italy) by means of stable isotopes and noble gas analysis

The chemistry and isotope ratios of He, C (δ¹³C) and H (δD) of free gases collected in the San Vittorino plain, an intramontane depression of tectonic origin, were determined to shed light on mantle degassing in central Italy. The C isotopic composition of CO₂ (δ¹³C–CO₂ −2.0‰ to −3.8‰) and He isotope ratios (R/R_A 0.12–0.27) were used to calculate the fraction of CO₂ originating from mantle degassing vs. sedimentary sources. The results show that CO₂ predominantly (average of 75%) derives from the thermo-metamorphic reaction of limestone. Between 6% and 22% of the CO₂ in the samples derives from organic-rich sedimentary sources. The mantle source accounts for 0–6% of the total CO₂; however, in two samples, located in proximity to the most important faults of the plain, the mantle accounts for 24% and 42%. The presence of faults and fractures allows upward gas migration from a deep source to the Earth’s surface, not only in the peri-Tyrrhenian sector, as generally reported by studies on natural gas emissions in central Italy, but also in the pre-Apennine and Apennine belts. Isotope ratios of CH₄ (δ¹³C–CH₄ −6.1‰ to −22.7‰; δD–CH₄ −9‰ to −129‰) show that CH₄ does not appear to be related to mantle or magma degassing, but it is the product of thermal degradation of organic matter (i.e. thermogenic origin) and/or the reduction of CO₂ (i.e. geothermal origin). Most of the samples appear to be affected by secondary microbial oxidation processes.     

Geochemistry and oxygen isotopic composition of olivine in kimberlites from the Arkhangelsk province: Contribution of mantle metasomatism

The paper presents data on the composition of olivine macrocrysts from two Devonian kimberlite pipes in the Arkhangelsk diamond province: the Grib pipe (whose kimberlite belongs to type I) and Pionerskaya pipe (whose kimberlite is of type II, i.e., orangeite). The dominant olivine macrocrysts in kimberlites from the two pipes significantly differ in geochemical and isotopic parameters. Olivine macrocrysts in kimberlite from the Grib pipe are dominated by magnesian (Mg# = 0.92–0.93), Ti-poor (Ti < 70 ppm) olivine possessing low Ti/Na (0.05–0.23), Zr/Nb (0.28–0.80), and Zn/Cu (3–20) ratios and low Li concentrations (1.2–2.0 ppm), and the oxygen isotopic composition of this olivine δ¹⁸O = 5.64‰ is higher than that of olivine in mantle peridotites (δ¹⁸O = 5.18 ± 0.28‰). Olivine macrocrysts in kimberlite from the Pionerskaya pipe are dominated by varieties with broadly varying Mg# = 0.90–0.93, high Ti concentrations (100–300 ppm), high ratios Ti/Na (0.90–2.39), Zr/Nb (0.31–1.96), and Zn/Cu (12–56), elevated Li concentrations (1.9–3.4 ppm), and oxygen isotopic composition δ¹⁸O = 5.34‰ corresponding to that of olivine in mantle peridotites. The geochemical and isotopic traits of low-Ti olivine macrocrysts from the Grib pipe are interpreted as evidence that the olivine interacted with carbonate-rich melts/fluids. This conclusion is consistent with the geochemical parameters of model melt in equilibrium with the low-Ti olivine that are similar to those of deep carbonatite melts. Our calculations indicate that the variations in the δ¹⁸O of the olivine relative the “mantle range” (toward both higher and lower values) can be fairly significant: from 4 to 7‰ depending on the composition of the carbonate fluid. These variations were formed at interaction with carbonate fluid, whose δ¹⁸O values do not extend outside the range typical of mantle carbonates. The geochemical parameters of high-Ti olivine macrocrysts from the Grib pipe suggest that their origin was controlled by the silicate (water–silicate) component. This olivine is characterized by a zoned Ti distribution, with the configuration of this distribution between the cores of the crystals and their outer zones showing that the zoning of the cores and outer zones is independent and was produced during two episodes of reaction interaction between the olivine and melt/fluid. The younger episode (when the outer zone was formed) likely involved interaction with kimberlite melt. The transformation of the composition of the cores during the older episode may have been of metasomatic nature, as follows from the fact that the composition varies from grain to grain. The metasomatic episode most likely occurred shortly before the kimberlite melt was emplaced and was related to the partial melting of pyroxenite source material.     

Did an extensive forest ever develop on the Chinese Loess Plateau during the past 130 ka?: a test using soil carbon isotopic signatures

Pleistocene vegetation history on the Chinese Loess Plateau has been traditionally investigated using palynological methods, and questions remain regarding whether an extensive broadleaf deciduous forest ever developed on the loess table under favorable climatic conditions. The authors have employed a C isotope approach to address this question by comparing δ¹³C values in soil organic matter from different loess ecological domains with known source vegetation to the C isotope values obtained from a paleosol section that can be dated back to 130 ka. The C isotopic compositions of modern soils from the loess table and the loess–desert transition gave δ¹³C values of −24.5‰ to −18.2‰ and −25.7‰ to −20.7‰, respectively. These C isotopic ratios are consistent with the standing modern vegetation that is dominated by a mixture of C₃ and C₄ plants and can be distinguished from that in the patchy forest areas where exclusive C₃ trees yield a narrow δ¹³C value range from −26.9‰ to −25‰ (average −26.1‰). Obtained δ¹³C compositions from paleosols and loess sediments in the Lantian and the Luochuan profiles vary from −24‰ to −16.9‰, indicating a grass-dominated steppe with shifting C₃ and C₄ contributions controlled mainly by paleoclimatic changes during the late Pleistocene. The present results suggest no extensive forest coverage on the loess table during the past 130 ka even under the most suitable conditions for forest development. This conclusion supports the explanation of natural causes for the development of only patchy forests on the modern loess table and provides critical historical information toward the vegetation restoration project that is currently underway on the Chinese Loess Plateau.     

Geochemical variations in the Cocos Plate subducting beneath Central America: implications for the composition of arc volcanism and the extent of the Galápagos Hotspot influence on the Cocos oceanic crust

New geochemical data from the Cocos Plate constrain the composition of the input into the Central American subduction zone and demonstrate the extent of influence of the Galápagos Hotspot on the Cocos Plate. Samples include sediments and basalts from Ocean Drilling Program (ODP) Site 1256 outboard of Nicaragua, gabbroic sills from ODP Sites 1039 and 1040, tholeiitic glasses from the Fisher Ridge off northwest Costa Rica, and basalts from the Galápagos Hotspot Track outboard of Central Costa Rica. Site 1256 basalts range from normal to enriched MORB in incompatible elements and have Pb and Nd isotopic compositions within the East Pacific Rise MORB field. The sediments have similar ²⁰⁶Pb/²⁰⁴Pb and only slightly more radiogenic ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb isotope ratios than the basalts. Altered samples from the subducting Galápagos Hotspot Track have similar Nd and Pb isotopic compositions to fresh Galápagos samples but have significantly higher Sr isotopic composition, indicating that the subduction input will have a distinct geochemical signature from Galápagos-type mantle material that may be present in the wedge beneath Costa Rica. Gabbroic sills from Sites 1039 and 1040 in East Pacific Rise (EPR) crust show evidence for influence of the Galápagos Hotspot ∼100 km beyond the morphological hotspot track.     

Carbon and oxygen isotopic compositions of Newania Dolomite Carbonatites, Rajasthan, India: implications for source of carbonatites

The Newania carbonatite complex of Rajasthan, India is one of the few dolomite carbonatites of the world, and oddly, does not contain alkaline silicate rocks thus providing a unique opportunity to study the origin and evolution of a primary carbonatite magma. In an attempt to characterize the mantle source, the source of carbon, and the magmatic and post-magmatic evolution of Newania carbonatites, we have carried out a detailed stable carbon and oxygen isotopic study of the complex. Our results reveal that, in spite of being located in a metamorphic terrain, these rocks remarkably have preserved their magmatic signatures in stable C and O isotopic compositions. The δ¹³C and δ¹⁸O variations in the complex are found to be results of fractional crystallization and low temperature post-magmatic alteration suggesting that like other carbonatites, dolomite carbonatites too fractionate isotopes of both elements in a similar fashion. The major difference is that the fractional crystallization of dolomite carbonatites fractionates oxygen isotopes to a larger extent. The modes of δ¹³C and δ¹⁸O variations in the complex, ?4.5?±?1‰ and 7?±?1‰, respectively, clearly indicate its mantle origin. Application of a multi-component Rayleigh isotopic fractionation model to the correlated δ¹³C versus δ¹⁸O variations in unaltered carbonatites suggests that these rocks have crystallized from a CO₂ + H₂O fluid rich magma, and that the primary magma comes from a mantle source that had isotopic compositions of δ¹³C ~ ?4.6‰ and δ¹⁸O ~ 6.3‰. Such a mantle source appears to be a common peridotite mantle (δ¹³C = ?5.0?±?1‰) whose carbon reservoir has insignificant contribution from recycled crustal carbon. Other Indian carbonatites, except for Amba Dongar and Sung Valley that are genetically linked to Reunion and Kerguelen plumes respectively, also appear to have been derived from similar mantle sources. Through this study we establish that dolomite carbonatites are generated from similar mantle source like other carbonatites, have comparable evolutionary history irrespective of their association with alkaline silicate rocks, and may remain resistant to metamorphism.     

Geochemistry, Monazite U–Pb Dating, and Li–Nd Isotopes of the Madi Rare Metal Granite in the Northeastern Part of the North China Craton

The Madi rare metal granite is a complex massif, which contains a variety of rare metals, such as Nb, Ta, Li, and Be. In this paper, the geochemical characteristics of the granite were obtained by multi-collector inductively coupled mass spectrometry (MC-ICP-MS). The precise crystalline age of the granite was obtained from monazite U-Pb dating, and the source of the granite was determined using Li-Nd isotopes. The Madi rare metal granite is a high-K (calc-alkaline), peraluminous, S-type granite. The U-Pb monazite age indicates that the crystalline age of the granite is 175.6 Ma, which is Early Jurassic. The granite is characterized by a relatively wide range of δ7Li values (+2.99‰ to +5.83‰) and high lithium concentrations (181 ppm to 1022 ppm). The lithium isotopic composition of the granite does not significantly correlate with the degree of magmatic differentiation. An insignificant amount of lithium isotope fractionation occurred during the granitic differentiation. The lithium isotopic composition of the granite significantly differs from that of the wall rock, but it is very similar to that of a primitive mantle peridotite xenolith (mean δ7Li value +3.5‰). The plot of Li concentration versus δ7Li indicates that the Li isotopic composition of the granite is similar to that of island arc lavas. Based on the above-described evidence, the granite was mainly derived from the crust, but it was contaminated by a deep granitic magma.     

Genesis and Metallogenic Process of the Lujing Uranium Deposit,Southwest Jiangxi Province,China: Constraints of Micropetrography and S–C–O Isotopes

The Lujing uranium deposit, located in the southeastern part of the Nanling metallogenic province, is one of the representative granite‐related hydrothermal uranium deposits in South China. Basic geology, geochemistry, and geochronology of the deposit have been extensively studied. However, there is still a chronic lack of systematic research on the genesis and metallogenic process of the deposit. Thus, we recently carried out an electron microprobe and stable isotopic analysis. The main research results and progresses are as follows: Uranium minerals in this deposit include coffinite, pitchblende, and uranothorite, and small amounts of uranium exist in accessory minerals in the form of isomorphism. Coffinite, which occurs predominantly as the pseudomorphs after pitchblende, also occurs as a primary mineral and is locally formed from the remobilization of uranium from adjacent uranium‐bearing minerals. The mineralizing fluid was originally composed of a magmatic fluid generated by late Yanshanian magmatism. The high As content of pyrite in ores may reflect the addition of meteoric water, or the formation water (or both), to the magmatic hydrothermal system. The δ³⁴S values vary from −14.4‰ to 13.9‰ (mean δ³⁴S = −3.9‰), showing a range that is similar to nearby Cambrian metamorphic strata and Indosinian granites, indicating that these host rocks represent the source of sulfur; however, the possibility of a mantle source cannot be completely ruled out. According to our new isotopic data and recent Pb isotopic data, we conclude that the uranium in ores was derived by leaching dominantly from the uranium‐rich host rocks, especially the Cambrian metamorphic strata. The δ¹³C_PDB values (−8.75‰ to 1.40‰; mean δ¹³C_PDB = −5.41‰) and δ¹⁸O_SMOW values (5.45–18.62‰; mean δ¹⁸O = 13.02‰) of reddish calcite from the ore‐forming stage suggest that the CO₂ in the mineralizing fluids was derived predominantly from the mantle, with a small component contributed by marine carbonates. Based on these new data and previous research results, this paper proposes that uranium metallogenesis in the Lujing deposit is closely associated with mafic magmatism resulting from crustal extension during the Cretaceous to Paleogene in South China.