Range Of Isotopic Compositions Research Articles

Characterizing lignin: Combining lignin phenol, methoxy quantification, and dual stable carbon and hydrogen isotopic techniques

Lignin is a major structural plant biochemical and biogeochemical compound present in peat and lignite. Its monomeric (phenolic) and polymeric structures include varying amounts of ether-bonded methyl groups (i.e., methoxy or OCH3). These methoxy groups are generally underused targets for both structural characterization and isotopic analyses. We analyzed the quantity and C and H isotopic composition of methoxy groups within a range of substrates including lignin phenols, lignin, wood, peat, lignite, and sub-bituminous and bituminous coal. We used the Zeisel method to cleave the ether bonds with hydroiodic acid to yield iodomethane which can be analyzed by gas chromatography (GC). Finding inconsistent transfer and isotope effects associated with room temperature headspace injections, we instead used isooctane as a solvent for the iodomethane analyte (the liquid method). Using the liquid method, we obtained a linear response by GC-flame ionization detection (GC-FID) for iodomethane and a linear calibration and 85 ± 6% recovery of methyl from methoxy groups from solid standards of phenolic compounds of known stoichiometry. We introduced quantification via lignin phenolic compounds to calibrate both analytical and experimental yield. Methyl yields provided structural information and confirmed that lignin oxidation products (LOPs) from copper oxide oxidation underestimate the number of methoxy-bearing phenols (yield < 0.3 of expected based on stoichiometry); in combination the two approaches provide structural information and quantification. We found that concentrations of methyl from methoxy groups in geologic sediments (lignite, sub-bituminous and bituminous coal) initially increase with diagenesis as lignin to cellulose ratio increases, and then decline to low concentrations during coalification, offering new possibilities for characterizing the transformation of peat and lignite. We assessed an array of plant biochemicals and established that natural and synthetic methoxy groups span a broad range of dual stable carbon and hydrogen isotopic compositions indicating scope for biogeochemical and forensic applications.

Syneruptive incorporation of martian surface sulphur in the nakhlite lava flows revealed by S and Os isotopes and highly siderophile elements: implication for mantle sources in Mars

Martian lava flows likely acquired S-rich material from the regolith during their emplacement on the planet’s surface. We investigated five of the twenty known nakhlites (Nakhla, Lafayette, Miller Range (MIL) 090032, Yamato 000593, and Yamato 000749) to determine whether these lavas show evidence of regolith assimilation, and to constrain the potential implications that this process has on chemical tracing of martian mantle source(s). To establish the proportionate influence of atmospheric, hydrothermal, and volcanic processes on nakhlite isotopic systematics we obtained in situ sulphur isotope data (Δ33S and δ34S) for sulphide grains (pyrrhotite and pyrite) in all five nakhlite samples. For Nakhla, Lafayette, and MIL 090032, these data are integrated with highly siderophile element (HSE) abundances and Os-isotope compositions, as well as textural information constrained prior to isotopic analysis. This work thereby provides the first Re-Os isotope systematics for two different nakhlites, and also the first Re-Os isotope data for martian sample for which detailed petrographic information was constrained prior to digestion.We report the largest variation in δ34S yet found in martian meteorites (−13.20‰ to +15.16‰). The relatively positive Δ33S and δ34S values of MIL 090032 (δ34S = +10.54 ± 0.09‰; Δ33S = −0.67 ± 0.10‰) indicate this meteorite assimilated sulphur affected by UV-photochemistry. In contrast, the strongly negative values of Lafayette (δ34S = −10.76 ± 0.14‰; Δ33S = −0.09 ± 0.12‰) are indicative of hydrothermal processes on Mars. Nakhla, Yamato 000593, and Yamato 000749 sulphides have a narrower range of sulphur isotope compositions (Δ33S and δ34S ∼ 0) that is consistent with no assimilation of martian surface materials during lava flow emplacement. Consequently we used this second group of Δ33S values to approximate the Δ33S of the nakhlite source, yielding a Δ33S value of −0.1‰.Nakhlite HSE patterns result from a sulphide-saturated melt where Ru-Os-Ir alloys/sulphide were likely crystallized during earlier phases of magmatic processing in Mars to result in the fractionated HSE patterns of the nakhlites. Our data, alongside a synthesis of previously published data, suggest assimilation of an enriched component to the primary nakhlite melt, potentially a late-stage crystallization cumulate from the martian magma ocean stage. In the context of this model, and within large uncertainties, our data hint at perturbation and potential decoupling of nakhlite Re-Os isotope systematics from other isotopic systems as a result of small degrees of assimilation of a regolith component with highly radiogenic 187Os/188Os.

Low-δ18O zircon xenocrysts in alkaline basalts; a window into the complex carbonatite-metasomatic history of the Zealandia lithospheric mantle

Abstract Megacrystic zircon grains from alkaline basaltic fields are rare but can provide fundamental insights into mantle metasomatic processes. Here, we report in-situ U-Pb ages, trace element concentrations and hafnium and oxygen isotopes for fourteen zircon megacrysts from two intraplate alkaline basalt locations in New Zealand. U-Pb ages indicate the zircons crystallised between 12.1 and 19.8 Ma. Zircon oxygen isotopic compositions range from low to mantle-like compositions (grain average δ18O = 3.8–5.1‰). Hafnium isotopes (eHf(t) = +3.3 to +10.4) mostly overlap with intraplate mafic rocks and clinopyroxene in metasomatized peridotitic mantle xenoliths but show no correlation with most trace element parameters or oxygen isotopes. The zircons are interpreted to have formed by the reaction between low-degree melts derived from pre-existing mantle metasomes and the depleted mantle lithosphere prior to eruption and transport to the surface. The low Hf concentration, an absence of Eu anomalies, and elevated U/Yb compared to Nb/Yb in the megacrystic zircons are interpreted to show that the source metasomes comprised subduction- and carbonatite-metasomatised lithospheric mantle. As these trace element characteristics are common for megacrystic zircon in intra-plate basaltic fields globally, they suggest the prevalence of subduction- and carbonatite-metsasomatised mantle under these intraplate volcanic regions. The unusually low δ18O was likely present prior to metasomatic enrichment and may have resulted from high-temperature hydrothermal alteration during initial mantle lithosphere formation at a mid ocean ridge or, possibly, during subduction-related processes associated with continent formation. The combination of proportionally varied contributions from carbonatite- and subduction-metasomatised lithospheric melts with asthenospheric melts may explain the variety of primitive intraplate basalt compositions, including low δ18O reported for some local intraplate lavas.

Silver isotope analysis of gold nuggets: An appraisal of instrumental isotope fractionation effects and potential for high-resolution tracing of placer gold

We describe a technique for high-precision analysis of 109Ag/107Ag ratios in natural and archaeological gold (1.0–120 mg/g Ag) with particular emphasis on the control of Ag yield and effects of instrumental mass bias. After dissolution of mg-sized gold samples in aqua regia and conversion to chlorides, a miniature column filled with the anion exchange resin AG@1-X8 was used for removal of Au from the sample solutions. In a second miniature column made of the Triskem TBP resin Ag was converted from the chloride to the nitrate form. Isotopic analyses on the MC-ICP-MS employed the combination of Pd-doping and standard bracketing and considering the measurements of replicate dissolutions and chromatographic separations for SRM978a and CEZAg reference solutions, the combined analytical uncertainty (2 s) of the analytical method is better than 0.016‰. A solution prepared from several gold nuggets was characterised isotopically (CEZAg with δ109Ag = 0.043 ± 0.015‰) for use as a silver-in‑gold reference material in Ag isotope studies of natural and processed gold.Results for gold nuggets from three continents indicate a wide variation in Ag concentrations (5 to 123 mg/g) and this is matched by an equally wide range in isotopic compositions (δ109Ag −0.58 to +0.83‰). This is larger than the variation found so far in in native gold from primary deposits (−0.42 to +0.5‰). Although small isotopic effects to lower δ109Ag during strong Ag loss are possible within a single grain, most analysed nuggets are internally isotopically homogeneous. This suggests preservation of the primary δ109Ag in the supergene environment and that gold was sourced from several distinct gold deposits in the catchment. Recent studies, however, indicate that even single primary deposits may be isotopically heterogeneous implying that Ag isotope fractionation is caused by numerous deposition-dissolution cycles in hydrothermal systems. Fine-grained detrital gold from three placers along the Rhine river in Germany show only small differences in δ109Ag (−0.005 ± 0.047 to +0.124 ± 0.007‰, despite being distributed along 480 km of river length. This may indicate thorough mixing of gold grain populations during transport.The small sample size required for Ag isotope work on gold opens the way for detailed micro-sampling approaches. These may be used to further examine the potential for within-grain isotopic variability related to fluviatile processing and can be used to correlate the composition of the placers with that of grains from primary sources.

Molybdenum isotope compositions of uranium ore concentrates by double spike MC-ICP-MS

The molybdenum (Mo) isotope composition of uranium ore concentrate (UOC) has been proposed as a nuclear forensic signature due to the ubiquitous presence of Mo in the nuclear fuel cycle and to the possibility that different UOC production pathways lead to characteristic Mo isotope fractionation. Furthermore, Mo forms a volatile hexafluoride which leads to the retainment of Mo in the nuclear fuel cycle through U enrichment and reactor operation processes. As a result, it is possible that the nuclear fuel cycle generates a rich array of Mo isotope signatures. The first step in interpreting Mo isotope signatures generated during the nuclear fuel cycle is to characterize the Mo isotope composition of starting materials. In this study, a suite of UOC samples were analyzed for their Mo isotope composition in order to constrain the range of Mo isotope compositions entering the front end of the nuclear fuel cycle. Analytical protocols were developed to purify Mo from a U rich matrix prior to Mo isotope analysis by double spike MC-ICP-MS. A >3‰ variation in the 98Mo/95Mo ratio was observed in the suite of UOC samples with δ98Mo ranging from −1.15 to +1.96‰ relative to the NIST 3134 Mo standard reference material. The δ98Mo range observed in the UOC samples is very similar to the δ98Mo range observed in crustal igneous rocks and Mo-bearing minerals, suggesting that Mo isotope variability in UOC is driven by variability in the parent U ores. However, Mo isotope fractionation during UOC production is evident with one of the UOC samples being isotopically heavy relative to its parent U ore by 0.75‰, suggesting that different UOC production processes also contribute to the total Mo isotope variability observed. Overall, it is expected that the Mo isotope signatures generated during enrichment and reactor process will be clearly discernible from those generated during UOC production.

Petrogenesis of the Middle Devonian syenites in the Miyun–Huairou Region of Beijing and its tectonic implications

Three Devonian magmatic rocks have been identified from the mid‐western part of the Yanshan Thrust‐and‐Fold Belt (YTFB). Here, we present new geochronological, Sr–Nd–Hf isotopic, and whole‐rock chemical data. Our new LA‐ICP‐MS U–Pb dating recognized syenite plutons of ca. 385 Ma, which include Laogongying, Shicheng, and Qiaomaiyu, respectively, around the Yunmeng Mountain in the Miyun–Huairou area of Beijing. Rocks from three plutons are characterized by low SiO2 and high alkali contents, especially high K2O, and they show syenite and foid syenite compositions. They display slight–middle light REE enrichment, no negative or positive Eu anomalies, strong depletion in Rb, Th, U, Nb, Ta, P, Zr, Hf, and Ti, enrichment in Ba, K, and Sr, low contents of Y and Yb, and high Sr/Y ratios. They have a relatively narrow range of isotopic compositions with initial 87Sr/86Sr ratios from 0.708203 to 0.710477, εNd(t) values from −12.26 to −13.28, and εHf(t) values from −19.92 to −17.96. This study shows the Middle Devonian intrusions were produced by fractional crystallization of a parental magma, which was derived by interaction between mantle‐derived alkaline magmas of a type I‐enriched mantle and pre‐existing continental crust. Tectonic background was likely emplaced in a back‐arc extension environment related to southward subduction of the Palaeo‐Asian oceanic plate or during the cessation of the subduction. Feldspar geothermometer and aluminium‐in‐hornblende barometry studies of the Middle Devonian plutons yielded emplacement temperature of ~700°C and pressure of ~6.5 kbar, indicating the emplacement depths of about 24 km. Combined with previous geobarometry results on the Middle Devonian plutons within the Inner Mongolia Palaeo‐uplift (IMPU) on the northern margin of the NCC, the strong uplift and exhumation the IMPU were identified during Middle Devonian to Late Triassic times. The exhumation was more than 4–5 km than those of the IMPU, resulting in widely absent of Palaeozoic strata within the YTFB.

Closing the loop: Subducted eclogites match thallium isotope compositions of ocean island basalts

Abstract Thallium (Tl) isotope compositions of ocean island basalts (OIBs) have been proposed as a novel tracer of subducted oceanic crust and sediments in ocean island basalt sources, which could act as direct confirmation that deep mantle recycling eventually resurfaces through mantle upwelling to form ocean island basalt magmatism. However, it is unknown if oceanic crust that went through an active subduction zone would retain the Tl isotope compositions recorded in hydrothermally altered oceanic crust and authigenic marine sediments. In this study we present Tl isotope and concentration data for samples of subducted oceanic crust from five different locations: Zambezi Belt, Zambia; Cabo Ortegal complex, Iberian Massif, Spain; Raspas Complex, southwest Ecuador; Syros island, Cyclades, Greece; Tian Shan, northwest China. Thallium concentrations in most samples follow strong linear relationships with K, Rb, Cs and Ba, which strongly suggest that the mineral phengite is the primary control of Tl abundances in subducted oceanic crust. This conclusion is consistent with recent Tl data sets for arc lavas that imply residual phengite in the arc lava source regions as a strong control of Tl recycling. We find that Tl isotope compositions vary widely and systematically in each location depending on the protolith, metamorphic and metasomatic history of the samples. Samples from Cabo Ortegal and Raspas Complex reveal Tl isotope compositions similar to their protoliths, which were comprised of low-temperature altered oceanic crust. Tian Shan metamorphic rocks and Zambian eclogites reveal invariant Tl isotope values indistinguishable from average mantle, which is best explained by overprinting by metamorphic fluids that contained high concentrations of Tl and other alkali metals. Samples from Syros reveal a range of Tl isotope compositions from normal mantle towards values for pelagic clay sediments. The sediment-like values in Syros likely arose from fluids released from the surrounding melange matrix that consists of serpentinite, metagabbros and metasediments. Each of the three Tl isotope ranges observed for subducted oceanic crust samples here are mirrored by individual OIB locations. Cabo Ortegal and Raspas Complex display Tl isotope compositions identical to St. Helena, suggesting that the HIMU component likely comprises subduction modified low-temperature altered oceanic crust. Thallium isotope ratios in Zambia and Tian Shan eclogites and blueschists are identical to lavas from Iceland, whereas Syros metamorphic rocks overlap almost exactly with lavas from Hawaii. Our data, therefore, show that Tl isotope compositions of oceanic crust and sediments can be traced through the subduction process and eventually is expressed largely unmodified in ocean island basalts.

Unique PGE–Cu–Ni Noril’sk Deposits, Siberian Trap Province: Magmatic and Tectonic Factors in Their Origin

The unique and very large PGE–Cu–Ni Noril’sk deposits are located within the Siberian trap province, posing a number of questions about the relationship between the ore-forming process and the magmatism that produced the traps. A successful answer to these questions could greatly increase the possibility of discovering new deposits in flood basalt provinces elsewhere. In this contribution, we present new data on volcanic stratigraphy and geochemistry of the magmatic rocks in the key regions of the Siberian trap province (Noril’sk, Taimyr, Maymecha-Kotuy, Kulyumber, Lower Tunguska and Angara) and analyze the structure of the north part of the province. The magmatic rocks of the Arctic zone are characterized by variable MgO (3.6–37.2 wt %) and TiO2 (0.8–3.9 wt %) contents, Gd/Yb (1.4–6.3) and La/Sm (2.0–10.4) ratios, and a large range of isotopic compositions. The intrusions in the center of the Tunguska syneclise and Angara syncline have much less variable compositions and correspond to a “typical trap” with MgO of 5.6–7.2 wt %, TiO2 of 1.0–1.6 wt %, Gd/Yb ratio of 1.4–1.6 and La/Sm ratio of 2.0–3.5. This compositional diversity of magmas in the Arctic zone is consistent with their emplacement within the paleo-rift zones. Ore-bearing intrusions (the Noril’sk 1, Talnakh, Kharaelakh) are deep-situated in the Igarka-Noril’sk rift zone, which has three branches, namely the Bolsheavamsky, Dyupkunsky, and Lower Tunguska, that are prospected for discovering new deposits. One possible explanation for the specific position of the PGE–Cu–Ni deposits is accumulation of sulfides in these long-lived zones from the Neoproterozoic to the Mesozoic era during magmatic and metamorphic processes. Thus, trap magmatism, itself, does not produce large deposits, but mobilizes earlier formed sulfide segregations in addition carrying metals in the original magmas. These deposits are the results of several successive magmatic events, in which emplacement of the traps was the final event.

Geochronology and isotope geochemistry studies of an epithermal gold deposit in the northern Lesser Khingan Range, NE China: The Gaosongshan example

The Gaosongshan epithermal gold (Au) deposit is located in the northern margin of the Lesser Khingan Range polymetallic ore belt, northeast (NE) China, and contains Au resources of more than 23 tons at an average grade of 6.3 g/t. Gold orebodies are mainly hosted in intensely altered volcanic rocks of the Lower Cretaceous Banzifang Formation, and as exploration has continued, gold has also been discovered in extensively altered porphyritic intrusions with the highest Au grade of 70 g/t. However, the ages of metallogenesis and related magmatism have not been well constrained yet, which have hindered the summary of metallogenic regularities. In this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U–Pb dating from the granite porphyry yields a weighted mean 206Pb/238U age of 101.6 ± 1.2 Ma, slightly older than the Rb–Sr isotope age of 98 ± 1.6 Ma for the auriferous quartz samples, indicating that the Gaosongshan Au mineralization is genetically related to the granite porphyry. The fluid δD and δ18OH2O values vary from −136% to −111% and from −9.3% to −2.5%, respectively, and the 4He and 40Ar isotope compositions range from 15.7 × 10−9 to 35.5 × 10−9 cm3 STP/g and 13.4 × 10−7 cm3 to 34.1 × 10−7 cm3 STP/g, respectively. The obtained isotopic data show that the ore-forming fluids were mixtures of magmatic and meteoric water but were dominated by meteoric water. The 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios of ores in the Gaosongshan deposit are 17.752–18.856, 15.514–15.674, and 38.005–39.921, respectively, which are similar to those of the Gaosongshan granite porphyry, implying that Pb and possibly Au originated primarily from late Early Cretaceous magmatic intrusions. Combining these results with data from previous studies, we propose that the Gaosongshan Au deposit formed in an extensional tectonic setting during the rollback of the Paleo-Pacific oceanic plate in NE China.

Nd and Sr isotopic composition of ancient iron‐made artifacts and ores from northwest Russia

AbstractIron‐made artifacts from northwest Russia, including nails, arrowheads, and brackets used in the 13th–19th centuries, have a wide range of Sr and Nd isotopic composition (87Sr/86Sr = 0.710–0.737 and 143Nd/144Nd = 0.5115–0.5124). Authigenic iron ore sites mined in the region from 10th to 19th centuries preserve a similar range of isotopic compositions, suggesting artifacts retain the Sr and Nd signatures of their parent ores. Analyses of the ores also reveal two broad regions distinguished by their isotopic compositions, with the Precambrian Baltic craton in the northern part of the region having very radiogenic Sr and unradiogenic Nd isotopic compositions (87Sr/86Sr &gt;0.7177 and 143Nd/144Nd &lt;0.5119) compared with ores from the Paleozoic sedimentary cover of the East European platform to the south. The recognition of distinct geochemical provinces permits identification of the broad regions from which the various ores were mined, and demonstrates the utility of applying radiogenic isotopic analyses to artifacts and their potential geologic sources.

Carbonaceous achondrites Northwest Africa 6704/6693: Milestones for early Solar System chronology and genealogy

Northwest Africa (NWA) 6704/6693 are medium- to coarse-grained achondrites with unique petrologic and geochemical traits that are distinct from the currently established meteorite groups. Here, we report on the extinct 26Al-26Mg and 53Mn-53Cr systems to establish fine-scale chronology of its formation and Cr and Ti isotopic anomalies to constrain the composition of the source reservoir of NWA 6704/6693. Excesses in the neutron-rich 54Cr and 50Ti isotopes, due to nucleosynthetic anomalies, separate NWA 6704/6693 from the vast majority of established achondrites and instead resemble the excesses seen among the carbonaceous chondrites; specifically, the CR-type chondrites. The excesses in these isotopes indicate a common feeding zone during accretion in the protoplanetary disk between the source of NWA 6704/6693 and that of the carbonaceous chondrites. The 26Al-26Mg data for pyroxene and plagioclase from NWA 6704 yield a (26Al/27Al)0 = (3.15 ± 0.38)×10−7 (MSWD = 0.49) and an initial δ26Mg∗ = −0.004 ± 0.005 at the time of isotopic closure. This initial (26Al/27Al)0 translates to an absolute age of 4563.14 ± 0.38 Ma, relative to the D’Orbigny angrite. However, given the potential heterogeneity of 26Al, the D’Orbigny angrite might not be a good age anchor for the purpose of calculating 26Al-26Mg ages. The 26Al-26Mg age relative to another carbonaceous achondrite, NWA 2976, is 4562.66 ± 0.60 Ma. The 53Mn-53Cr systematics of NWA 6704/6693 indicate a (53Mn/55Mn)0 of (2.59 ± 0.34) × 10−6 (MSWD = 1.2) with an evolved initial ε53Cr of +0.14 ± 0.03. The (53Mn/55Mn)0 yields an 53Mn-53Cr age of 4562.17 ± 0.76 Ma relative to the D’Orbigny angrite. Concordant ages determined using the short-lived 26Al-26Mg and 53Mn-53Cr systems and extant 207Pb-206Pb system (4562.60 ± 0.30 Ma for NWA 6704/6693; Amelin et al., 2019) indicate rapid cooling and nearly contemporaneous closing of multiple isotope systems. The ancient crystallization ages and positive 54Cr and 50Ti anomalies of NWA 6704/6693 indicate widespread melting and differentiation processes occurring in both non-carbonaceous (NC) and carbonaceous chondrite (CC) regions of the protoplanetary disk. Additionally, we report the Cr and Ti isotopic composition for a petrologic range of CR-type materials (CR2, CR6, and achondrites). The additional Cr and Ti isotopic data for these CR-type materials indicates a range in isotopic composition not previously observed based on CR2 chondrites alone.

Source of copper in the giant Shimensi W-Cu-Mo polymetallic deposit, South China: Constraints from chalcopyrite geochemistry and oxygen fugacity of ore-related granites

Porphyry-type copper mineralization is generally considered to be related to ore-forming fluid exsolution from oxidized, magnetite-bearing intermediate- to felsic magmas. However, copper deposits associated with ilmenite-bearing per-aluminous evolved granites also exist and their origin remains obscure. The Shimensi W-Cu-Mo polymetallic deposit, located in the northern segment of the Jiangnan Orogen (South China) composed mainly of the Neoproterozoic Shuangqiaoshan Group meta-sediments/volcanic rocks and biotite granite, is one of the largest tungsten deposits in the world. The W-Cu-Mo polymetallic orebodies occur at the contact zone between the Mesozoic ilmenite-bearing, fluorite-bearing F-rich highly fractionated granite and the Neoproterozoic granite. The reason for the accompanying Cu mineralization within ilmenite-bearing granites is unclear. In this paper, we present a detailed study of chalcopyrite geochemistry including S-Pb isotopes, trace elements and Nd isotopes, and oxygen fugacity (fO2) of ore-related granites in the Shimensi deposit to constrain the origin of copper.Sulfur isotope values of the sulfides give a narrow δ34S interval of −3.3 to −0.5‰ (mean = −1.5‰, n = 32), suggesting the ore-forming fluid is of magmatic origin. The similarity of Pb isotopes of the majority of sulfides and K-feldspars from Mesozoic granites indicates their genetic relationship. However, chalcopyrite samples show a wider range of Pb isotopic compositions than that of K-feldspars, suggesting an extra source for the ore-forming fluids. Chalcopyrite from the ore deposit show features of LREE–enriched patterns, variable Eu negative anomalies (Eu/Eu∗ = 0.26–0.75) and (La/Sm)N values (0.77–5.93), while the two figures for the Mesozoic F-rich evolved granites are Eu/Eu∗ = 0.18–0.45 and (La/Sm)N = 2.42–4.09. This, along with and the larger range of εNd values (−12.4 to −2.7) of the chalcopyrites than for the Mesozoic granites and Neoproterozoic granite therein (−8.6 to −6.2), suggest that the ore-forming fluids cannot be attributed to the Mesozoic granites alone. The local Cu-enriched Neoproterozoic Shuangqiaoshan Group rocks should have contributed to the mineralization. The low bulk rocks Fe3+/Fe2+ ratios (0.02–1.00, average 0.22), Fe2+-enriched biotite compositions (Fe2+/Fe3+ = 5.64–143, average 22), combined with the low Ce4+/Ce3+ ratios (3–509, average 142), negative Eu anomalies (Eu/Eu∗ = 0.05–0.56, average 0.25), and low fO2 [△FMQ-3.4 (±1.9)-△FMQ + 1.5 (±1.7)] for the Mesozoic magmatic zircons, suggest that the granites in the Shimensi deposit are relatively reduced. The low oxygen fugacity (below NNO) of granites is favorable for significant tungsten mineralization accompanying by minor Cu mineralization.

Ore Genesis and Tectonic Significance of the Xiaojiashan Tungsten Deposit, Eastern Tianshan, Xinjiang, China: Evidence from Geology, Fluid Inclusions, and Stable Isotope Geochemistry

AbstractThe Xiaojiashan tungsten deposit is located about 200 km northwest of Hami City, the Eastern Tianshan orogenic belt, Xinjiang, northwestern China, and is a quartz vein‐type tungsten deposit. Combined fluid inclusion microthermometry, host rock geochemistry, and H–O isotopic compositions are used to constrain the ore genesis and tectonic setting of the Xiaojiashan tungsten deposit. The orebodies occur in granite intrusions adjacent to the metamorphic crystal tuff, which consists of the second lithological section of the first Sub‐Formation of the Dananhu Formation (D2d 12). Biotite granite is the most widely distributed intrusive bodies in the Xiaojiashan tungsten deposit. Altered diorite and metamorphic crystal tuff are the main surrounding rocks. The granite belongs to peraluminous A‐type granite with high potassic calc‐alkaline series, and all rocks show light Rare Earth Element (REE)‐enriched patterns. The trace element characters suggest that crystallization differentiation might even occur in the diagenetic process. The granite belongs to postcollisional extension granite, and the rocks formed in an extensional tectonic environment, which might result from magma activity in such an extensional tectonic environment. Tungsten‐bearing quartz veins are divided into gray quartz vein and white quartz veins. Based on petrography observation, fluid inclusions in both kinds of vein quartz are mainly aqueous inclusions. Microthermometry shows that gray quartz veins have 143–354°C of Th, and white quartz veins have 154–312°C of Th. The laser‐Raman test shows that CO2 is found in fluid inclusions of the tungsten‐bearing quartz veins. Quadrupole mass spectrometry reveals that fluid inclusions contain major vapor‐phase contents of CO2, H2O. Meanwhile, fluid inclusions contain major liquid‐phase contents of Cl−, Na+. It can be speculated that the ore‐forming fluid of the Xiaojiashan tungsten deposit is characterized by an H2O–CO2, low salinity, and H2O–CO2–NaCl system. The range of hydrogen and oxygen isotope compositions indicated that the ore‐forming fluids of the tungsten deposit were mainly magmatic water. The ore‐forming age of the Xiaojiashan deposit should to be ~227 Ma. During the ore‐forming process, the magmatic water had separated from magmatic intrusions, and the ore‐bearing complex was taken to a portion where tungsten‐bearing ores could be mineralized. The magmatic fluid was mixed by meteoric water in the late stage.

Lead isotope mapping of galena from base metal deposits in the southern Korean Peninsula

The purpose of this study is to investigate the differences in sources of discrete four zones that are represented by the lead isotope map of metal mines using galena samples. The lead isotope map has been constructed based on 119 galena samples from 38 metal mines in the southern Korean Peninsula, together with previously published data, using spatial and zoning distribution analysis. The spatial pattern of 206Pb/204Pb ratio shows relatively dense distribution with highest value at the northeastern region, while 207Pb/204Pb and 208Pb/204Pb ratios are the lowest at the southeastern region. These results indicate possible subdivision of the lead isotope maps based on geotectonic subdivisions and geographical locations of the Korean Peninsula. This subdivision has been checked by linear discriminant analysis (LDA). The range of lead isotopic composition for zone 1 has fairly homogeneous values (206Pb/204Pb = 18.156–18.591, 207Pb/204Pb = 15.482–15.644, and 208Pb/204Pb = 37.870–38.768), and are geographically similar to the Gyeongsang Basin. Lead isotopic compositions of zone 2 show the highest ratios (206Pb/204Pb = 18.625–20.483, 207Pb/204Pb = 15.708–16.068, 208Pb/204Pb = 37.734–40.463) in the southern Korean Peninsula, that are geographically corresponding to the Taebaeksan Basin and the northeastern Yeongnam Massif. Relatively lower values (206Pb/204Pb = 17.149–17.817, 207Pb /204Pb = 15.497–15.731, 208Pb /204Pb = 37.847–39.773) along the western Gyeonggi Massif are grouped as zone 4, while the rest of the areas, including the Okcheon metamorphic belt, most of the Gyeonggi Massif, and the Yeongnam Massif, might represent zone 3. The results clearly indicate the possible differences in the source reservoirs that are similar to the geotectonic provinces of the Korean Peninsula.

Geochemistry of deep Manihiki Plateau crust: Implications for compositional diversity of large igneous provinces in the Western Pacific and their genetic link

Geochemical studies revealed two major (high- and low-Ti) magmatic series composing the Manihiki Plateau in the Western Pacific. Here we report new geochemical data (major and trace element and Sr-Nd-Pb isotope compositions) of the Manihiki rocks. The rocks belong to the previously rarely sampled high-Ti Manihiki series and represent a section of deep crust of the plateau. The rocks were collected by remotely operated vehicle ROV Kiel 6000 during R/V SONNE SO225 expedition from a tectonic block at a stretched and faulted boundary between the Northern and Western Manihiki sub-plateaus. Additional data is presented on samples obtained by dredging during the same cruise. Judging from the age of stratigraphically higher lavas, most samples must be ≥125 Ma old. They comprise fully crystalline microdolerites, aphyric and Ol-Px-Pl-phyric basalts and breccias metamorphosed under greenschist to amphibolite facies with peak metamorphic temperatures of 636–677 °C and pressures of 2.0–2.7 kbar. A single sample of hornblende gabbro was also recovered and likely represents a late stage intrusion. Despite strong metamorphism, the samples from the ROV profile reveal only minor to moderate chemical alteration and their initial compositions are well preserved. The rocks are relatively primitive with MgO up to 13 wt%, range from enriched to depleted in LREE (LaN/SmN = 0.7–1.1), exhibit variable but mostly depleted Nb contents (Nb/Nb* = 0.8–1.3) and display only a narrow range in isotope compositions with strong EM1 characteristics (εNd (t) = 1.8–3.6, 206Pb/204Pb (t) = 17.9–18.1, 207Pb/204Pb (t) = 15.49–15.53, 208Pb/204Pb (t) = 38.08–38.42). The parental magmas are interpreted to originate from a thermochemical plume with a potential mantle temperature >1460 °C. The trace element and isotope EM1 signature of the high-Ti rocks reflects the presence of recycled lower continental crust material or re-fertilized subcontinental lithospheric mantle in the plume source. A highly refractory mantle was the primary source of the low-Ti basalts and could also contribute to the origin of high-Ti basalts. On average a more depleted mantle source for the Manihiki rocks can explain ~30% lower crustal thickness of this plateau compared to Ontong Java Plateau, which was mainly formed by melting of similarly hot but more fertile mantle. The presently available data suggest that the sources of Ontong Java and Manihiki Plateaus were compositionally different and could represent two large domains of a single plume or two contemporaneous but separate plumes.

Palaeohydrogeology using geochemical, isotopic and mineralogical analyses: Salinity and redox evolution in a deep groundwater system through Quaternary glacial cycles

Mineralogical, geochemical and isotopic analyses of secondary calcites are interpreted as part of an investigation of deep groundwaters in fractured metavolcanic rock overlain by sedimentary rock. Drillcore rock samples and groundwater samples from deep boreholes (maximum depth 1950 m) were analysed. This produces information about the evolution of salinity and redox in relation to past groundwater movements including the impacts of climatic change through the Quaternary period.Salinities of present-day groundwaters vary from dilute to brine concentrations and are related to three distinct groundwater flow regimes. Crystal morphology, stable isotopic analyses and isotopic dating, cathodoluminescence and microanalyses of Fe, Mn and REEs in the latest generation of secondary calcite, plus other analyses, have provided insights into variations of salinity over time and of redox in past groundwaters. Interpretation suggests that groundwater in the depth range of the transition from dilute to brackish/saline concentrations has been gradually diluted over time by meteoric water ingress. 230Th/234U whole-crystal ages indicate that at least part of the late-stage calcite mineralisation in the present groundwater flow system is of Quaternary age, although the mineralisation may have been initiated much earlier by meteoric invasion in the Miocene, following regional uplift. The calcites exhibit a wide range in oxygen isotope composition (δ18OPDB −2 to −22‰), although no extremely light or heavy δ13C values indicative of microbial methane oxidation or deep methanogenesis were observed. The very light δ18O values suggest that glacial or other cold-climate waters flowed to more than 700 m depth in the centre of the study area and formed a greater proportion of groundwater at that depth than at present.Fe and Ce are interpreted as semi-quantitative proxies for past redox conditions over the period when secondary calcite was deposited. Variability of Fe and Mn contents of secondary calcites in deeper rock, presently containing saline groundwater, is evidence of reducing conditions being maintained in the long term, though the strength of negative redox has probably fluctuated due to other redox-active chemistry. Depth-wise changes of groundwater redox in the past are also indicated by Ce concentrations versus other REEs in secondary calcites. Shallow calcites show a negative Ce anomaly in some growth zones due to oxidation to CeIV whilst deeper calcites do not exhibit this Ce behaviour, indicating that reducing conditions prevailed. Distribution of Fe-Mn oxyhydroxides and pyrite confirm, at a broader scale over depth and time, the findings about redox variations that secondary calcites indicate.Mineralogical and geochemical studies add further information to the understanding of past geochemical conditions in deep groundwaters in this area. Interpretations provide semi-quantitative constraints on the evolution and likely variations and directions of movement of groundwater salinity and redox over the Quaternary timescale.

Preglacial palaeoenvironmental evolution of the Ediacaran Loma Negra Formation, far southwestern Gondwana, Argentina

The Ediacaran Loma Negra Formation may be deposited in a platform environment related to the Clymene Ocean. This unit is exposed in the Olavarría and Barker areas within the Tandilia Basin, and composed entirely of lime mudstones (∼40 m thick). The age of the Loma Negra Formation (LNF), the uppermost unit of the Sierras Bayas Group, has been debated, but it should be older than 560 Ma (age of the overlying succession) and younger than 600 Ma (age of the underlying iron-rich mudstone of the Colombo Formation). This extended carbonate platform (>100 km) is divided into two sedimentary facies: one related to the basal section, in which lime mud originated by suspension fall-out in an open-marine ramp (reddish or greenish limestones), and the other facies represented by black to dark grey limestones from the middle and upper sections. The LNF limestones studied, obtained from five sections near the Olavarría and Barker areas, reveal constant curves of positive δ13C values (∼+2 to +4%), similar to those recorded in other middle-Ediacaran marine proxies worldwide. Our sedimentological and geochemical study of the LNF sections shows extraordinarily consistent carbon and oxygen isotope trends that may be useful for detailed intrabasinal correlations. Samples of the LNF fabric-retentive micrite preserve an unusually narrow range of oxygen isotope compositions, which is consistent with potential climatic variation, considering the multi-proxies retained. A subsequent decrease in carbonate primary productivity and an increase in siliciclastic supply are associated with the negative δ13C trend in the overlying unit, at the base of the La Providencia Group. This negative excursion in δ13C from +2.8 to −3.6% is also regarded as a response to the cooling and sea-level fall probably linked to the Gaskiers glaciation. Furthermore, such data are consistent with late-Ediacaran carbonates from other Neoproterozoic successions.Strontium isotope ratios in limestones (0.7060–0.7070) should reflect the near-primary strontium isotope composition of the original seawater, particularly regarding the strontium content (∼300 ppm) and the Rb/Sr ratios (≤0.001) of primary micrite, consistent with a seawater origin. Strontium isotope data reaches 0.7082 with an Rb/Sr ratio of 0.001–0.006.

Experimental investigation on the controls of clumped isotopologue and hydrogen isotope ratios in microbial methane

The abundance of methane isotopologues with two rare isotopes (e.g., 13CH3D) has been proposed as a tool to estimate the temperature at which methane is formed or thermally equilibrated. It has been shown, however, that microbial methane from surface environments and from laboratory cultures is characterized by low 13CH3D abundance, corresponding to anomalously high apparent 13CH3D equilibrium temperatures. We carried out a series of batch culture experiments to investigate the origin of the non-equilibrium signals in microbial methane by exploring a range of metabolic pathways, growth temperatures, and hydrogen isotope compositions of the media. We found that thermophilic methanogens (Methanocaldococcusjannaschii, Methanothermococcus thermolithotrophicus, and Methanocaldococcus bathoardescens) grown on H2 + CO2 at temperatures between 60 and 80 °C produced methane with Δ13CH3D values (defined as the deviation from stochastic abundance) of 0.5–2.5‰, corresponding to apparent 13CH3D equilibrium temperatures of 200–600 °C. Mesophilic methanogens (Methanosarcina barkeri and Methanosarcina mazei) grown on H2 + CO2, acetate, or methanol produced methane with consistently low Δ13CH3D values, down to −5.2‰. Closed system effects can explain part of the non-equilibrium signals for methane from thermophilic methanogens. Experiments with M. barkeri using D-spiked water or D-labeled acetate (CD3COO−) indicate that 1.6–1.9 out of four H atoms in methane originate from water, but Δ13CH3D values of product methane only weakly correlate with the D/H ratio of medium water. Our experimental results demonstrate that low Δ13CH3D values are not specific to the metabolic pathways of methanogenesis, suggesting that they could be produced during enzymatic reactions common in the three methanogenic pathways, such as the reduction of methyl-coenzyme M. Nonetheless CH bonds inherited from precursor methyl groups may also carry part of non-equilibrium signals.

Tracing natural and industrial contamination and lead isotopic compositions in an Australian native bee species

This study investigates trace element concentrations (arsenic (As), manganese (Mn), lead (Pb) and zinc (Zn)) and Pb isotopic compositions in an Australian native bee species, Tetragonula carbonaria, and its products of honey and wax. Co-located soil and dust samples were simultaneously analysed with the objective of determining if the bees or their products had potential application as a proxy for monitoring environmental contamination. The most significant relationships were found between Pb concentrations in honey (r = 0.814, p = 0.014) and wax (r = 0.883, p = 0.004) and those in co-located dust samples. In addition, Zn concentrations in honey and soil were significantly associated (r = 0.709, p = 0.049). Lead isotopic compositions of native bee products collected from background sites adjacent to Sydney national parks (206Pb/207Pb = 1.144, 208Pb/207Pb = 2.437) corresponded to local geogenic rock and soil values (206Pb/207Pb = 1.123–1.176, 208Pb/207Pb = 2.413–2.500). By contrast, inner Sydney metropolitan samples, including native bees and wax (206Pb/207Pb = 1.072–1.121, 208Pb/207Pb = 2.348–2.409), co-located soil and dust (206Pb/207Pb = 1.090–1.122, 208Pb/207Pb = 2.368–2.403), corresponded most closely to aerosols collected during the period of leaded petrol use (206Pb/207Pb = 1.067–1.148, 208Pb/207Pb = 2.341–2.410). A large range of Pb isotopic compositions in beehive samples suggests that other legacy sources, such as Pb-based paints and industrials, may have also contributed to Pb contamination in beehive samples. Native bee data were compared to corresponding samples from the more common European honey bee (Apis mellifera). Although Pb isotopic compositions were similar in both species, significant differences in trace element concentrations were evident across the trace element suite, the bees and their products. The statistical association between T. carbonaria and co-located environmental contaminant concentrations were stronger than those in European honey bees, which may be attributable to its smaller foraging distance (0.3–0.7 km versus 5–9 km, respectively). This implies that T. carbonaria may be more suitable for assessing small spatial scale variations of trace element concentrations than European honey bees.

Noble gas geochemistry of fluid inclusions in South African diamonds: implications for the origin of diamond-forming fluids

Fibrous diamond growth zones often contain abundant high-density fluid (HDF) inclusions and these provide the most direct information on diamond-forming fluids. Noble gases are incompatible elements and particularly useful in evaluating large-scale mantle processes. This study further constrains the evolution and origin of the HDFs by combining noble gas systematics with δ13C, N concentrations, and fluid inclusion compositions for 21 individual growth zones in 13 diamonds from the Finsch (n = 3), DeBeers Pool (n = 7), and Koffiefontein (n = 3) mines on the Kaapvaal Craton. C isotope compositions range from −2.8 to −8.6‰ and N contents vary between 268 and 867 at.ppm, except for one diamond with contents of <30 at.ppm N. Nine of the thirteen studied diamonds contained saline HDF inclusions, but the other four diamonds had carbonatitic or silicic HDF inclusions. Carbonatitic and silicic HDFs yielded low He concentrations, R/Ra (3He/4Hesample/3He/4Heair) values of 3.2–6.7, and low 40Ar/36Ar ratios of 390–1940. Noble gas characteristics of carbonatitic-silicic HDFs appear consistent with a subducted sediment origin and interaction with eclogite. Saline HDFs are characterised by high He concentrations, with R/Ra mostly between 3.9 and 5.7, and a wide range in 40Ar/36Ar ratios (389–30,200). The saline HDFs likely originated from subducted oceanic crust with low He but moderate Ar contents. Subsequent interaction of these saline HDFs with mantle peridotite could explain the increase in He concentrations and mantle-like He isotope composition, with the range in low to high 40Ar/36Ar ratios dependent on the initial 36Ar content and extent of lithosphere interaction. The observed negative correlation between 4He contents and R/Ra values in saline HDFs indicates significant in situ radiogenic 4He production.