Major Isotope Research Articles

Hydrogeochemical characteristics of hot springs in the Daju Fault Zone of the SE Tibetan Plateau, China

Tests on 31 water samples from 10 hot springs within the Daju Fault Zone were conducted to evaluate thermal hydrogeochemical processes in terms of reservoir temperature and depth, circulation length, and relationships with seismic activity. Major elements, trace elements, hydrogen and oxygen isotopes as well as strontium isotopes were analyzed. Results show that the hot spring waters could be sub-divided into nine distinct hydrogeochemical types, receiving recharge primarily from meteoric water and snow-mountain meltwater at elevations ranging between 2262.4 and 4122.1 m above sea level (a.s.l.). Additionally, these springs display a wide range of cold-water mixing ratios (ranging from 60 % to 96 %), reservoir temperatures (ranging between 54.4 and 132.3 °C), as well as circulation depths spanning across a range of values (from 1950.8 to 5337.1 m). Ca2+ /Na+, Mg2+ /Na+ and HCO3–/Na+ ratios suggest that hydrogeochemical processes governing geothermal water composition are controlled by interactions between CO2-enriched fluids and surrounding lithologies, along with cation exchange. The relationship between Cl− and K+, B, Li+ indicates their distinct origins from disparate deep fluids. Other elements in hot spring waters of this region are generally originated from rock weathering, and they vary significantly with different geological conditions. Through years of continuous sampling analysis, it has been observed that TDS, HCO3–, and (Ca2++Mg2+) in hot springs HTX, TSQ, and XG1 exhibit significant variations before and after earthquakes, rendering them highly suitable for investigating the correlation between seismic activity and hydrogeochemistry, whereas CQG excels as the premier option for observing temperature variations caused by seismic activities.

Genesis of Triassic Buziwannan Granites in the West Kunlun Orogen Belt, China: Constraints from in Situ Major, Trace and Sr Isotope Analyses of Plagioclase

Genesis of Triassic Buziwannan Granites in the West Kunlun Orogen Belt, China: Constraints from in Situ Major, Trace and Sr Isotope Analyses of Plagioclase

Evidence for isotopically light Fe mobility under oxidising conditions in subduction zone fluids: A record of Monviso meta-serpentinites, Western Alps

The isotopically light Fe signature of arc magmas relative to mid-oceanic ridge basalts (MORB) is expected to be related to the redox state of their source. This implies a link between Fe mobility and redox variations across subduction zones. Here we address slab chemical variations during prograde metamorphism through a comprehensive geochemical study, including major, trace elements and Fe stable isotope (δ56Fe) analyses, of meta-serpentinites composing the eclogitic meta-ophiolite of the Monviso massif (Western Alps, Italy). These rocks partly preserve mantle related geochemical heterogeneities, as supported by negative correlations between fluid immobile elements (High Field Strong Elements) and LREE/HREE (Light – Heavy Rare Earth Elements) ratios. They are however characterized by large Cs enrichments relative to U or alkali elements suggesting that abyssal fluid mobile elements signature was overprinted by subduction related processes. Meta-serpentinites display large δ56Fe variations, from -0.20 ± 0.05 ‰ to +0.09 ± 0.03 ‰. Mineral separate analyses of olivine bearing veins show low Δ56Fe between olivine and magnetite (∼ 0.4 ‰), which according to Fe isotope thermometry correspond to high temperature equilibration, estimated between 530 and 550 °C, compatible with Monviso metamorphic climax (520–570 °C and 2.6–2.7 GPa). These results, in combination with geochemical modelling, confirm a reset of δ56Fe signature of abyssal serpentinites during prograde metamorphism in subduction zones. The bulk rock δ56Fe values of Monviso meta-serpentinites are negatively correlated with their Fe3+/∑Fe and As concentrations (a redox-sensitive and fluid mobile element). These correlations can be attributed to a metasomatism by external fluids derived from slab serpentinites during subduction. It also concords with the oxygen fugacity (fO2) record in meta-serpentinites, with meta-serpentinites equilibrated at high fO2 displaying the lowest δ56Fe values while samples equilibrated at low fO2 display mantle like δ56Fe signatures. These results highlight that oxidising conditions during serpentinite dehydration are likely to boost isotopically light Fe mobility in slab derived fluids.

Petrographic and Geochemical Evidence for a Complex Magmatic Plumbing System beneath Bagana Volcano, Papua New Guinea

Abstract Bagana is a persistently active stratovolcano located on Bougainville Island, Papua New Guinea. Characteristic activity consists of prolonged lava effusion over months to years, with occasional shifts to explosive vulcanian or sub Plinian eruptions that threaten surrounding communities. Satellite observations have shown that Bagana is a major SO2 emitter, particularly during eruptive intervals. Despite persistent and potentially hazardous activity, no previous geophysical, petrological, or geochemical studies have constrained the magma storage conditions and reservoir processes at Bagana. To address this knowledge gap, we present new bulk rock major, trace element, and radiogenic isotope data, plus mineral phase major element compositions, for Bagana lavas erupted in 2005 and 2012 and ash erupted in 2016. We use our new data to understand the magmatic processes controlling the typical effusive activity and provide the first estimates of magma storage conditions beneath Bagana. The basaltic andesite bulk rock compositions (56–58 wt% SiO2) of our Bagana lavas reflect accumulation of a plagioclase + clinopyroxene + amphibole + magnetite + orthopyroxene crystal cargo by andesitic-dacitic (57–66 wt% SiO2) carrier melts. Constraints from clinopyroxene and amphibole thermobarometry, amphibole hygrometry, and experimental petrology suggest that the high-An plagioclase + clinopyroxene + amphibole + magnetite assemblage crystallizes from basaltic-basaltic andesite parental magmas with >4 wt% H2O, over a temperature interval of ~1100–900°C, at pressures of ~130–570 MPa, corresponding to ~5–21 km depth. Continued crystallization in the magma storage region at ~5–21 km depth produces andesitic to dacitic residual melts, which segregate and ascend towards the surface. These ascending melts entrain a diverse crystal cargo through interaction with melt-rich and mushy magma bodies. Degassing of carrier melts during ascent results in crystallization of low-An plagioclase and the formation of amphibole breakdown rims. The radiogenic isotope and trace element compositions of Bagana lavas suggest that parental magmas feeding the system derive from an enriched mantle source modified by both slab fluids and subducted sediments. Our findings suggest that the prolonged lava effusion and persistently high gas emissions that characterise Bagana’s activity in recent decades are sustained by a steady state regime of near-continuous ascent and degassing of magmas from the crustal plumbing system. Our characterisation of the Bagana magmatic plumbing system during effusive activity provides a valuable framework for interpreting ongoing monitoring data, and for identifying any differences in magmatic processes during any future shift to explosive activity.

Application of ATONA Amplifiers to the Measurement of Uranium Isotopic Ratios by Thermal Ionization Mass Spectrometry.

Uranium isotopic composition can provide valuable information about the history and provenance of a nuclear material; therefore, uranium isotopic analyses are frequently made in the nuclear forensics, safeguards, and environmental monitoring communities. These measurements have always presented challenges due to the extreme variability in the relative abundance between the major (235U, 238U) and minor (233U, 234U, 236U) isotopes of uranium. The recently developed ATONA (Atto- to Nano-Amp) amplification system paired with Faraday cup detectors has a large dynamic range and low noise floor making it ideal for measuring uranium isotopic ratios in materials of both natural and anthropogenic origin. A wide variety of certified reference materials were analyzed to investigate the utility of the ATONA amplification system for determining uranium isotopic composition in samples ranging from depleted to highly enriched. The ATONA amplifiers provide nearly an order of magnitude improvement in external reproducibility over 1011 Ω amplifiers when measuring the minor 234U/238U ratio in isotopically natural and depleted samples and when paired with a secondary electron multiplier can measure very low relative abundance uranium isotopes (i.e., 236U).

Investigating hydrological dynamics and mean residence times of springs in the Tawi catchment, India: Insights into recharge mechanisms and water source variability

This study investigates the hydrological dynamics and Mean Residence Times (MRTs) of springs in the Tawi catchment, India, aiming to elucidate recharge mechanisms and water source variability. The catchment's characteristics, including altitude, geology, and land use, are examined in relation to isotopic composition and residence times of springs at six distinct locations. The study examines seasonal variations in isotopic signatures of precipitation, revealing distinct patterns during Western Disturbances (WDs) and Indian Summer Monsoon (ISM). In addition, a composite δ18O – δ2H regression line (LMWL) is developed, that suggests significant secondary evaporation from falling raindrops as a major process shaping precipitation isotopes in the catchment. The isotopic data from six stations within the catchment demonstrate specific variations influenced by local factors. Enriched rain samples in urban areas like Udhampur and Jammu show higher secondary evaporation, while depleted samples in Chenani and Mantalai suggest a canopy cover influence. Temporal and spatial variations in spring water isotopes suggest either a consistent recharge source or isotopic damping. Mean Residence Times (MRTs) of springs indicate variations in aquifer characteristics, with longer MRTs in Chenani and Mantalai indicating deeper and more complex systems. Moderate MRTs in Pangara Jagir, and Udhampur springs, suggest a balance between storage and recharge. Hydrograph separation analysis demonstrates the dominance of WDs as the precipitation source, except for Chak Rakwal, which exhibits karstified behavior with significant contribution during the ISM. The study underscores the importance of understanding recharge elevations and delineating recharge zones for sustainable groundwater management and preservation of water quality in the Tawi catchment. By elucidating these critical aspects, the study contributes to informed decision-making and effective water resource management in complex catchment areas.

Geochemistry of hydrothermal illitizations in Eocene Kösedağ magmatic rocks, Zara-Suşehri area, NE Sivas, East-Central Anatolia: Origin and age of alteration

The study area located at the periphery of the collision zone between the Eurasian plate (i.e. Pontides) and Tauride-Anatolide platform, NE of Sivas in the east-central Turkey, which is part of the Tethyan Metallogenic Belt. Mixed-layer illite-smectite (IS) and illite minerals are derived within the hydrothermal alteration zones with a few km2 surface areas (up to 30 km2) in Eocene volcanic and plutonic rocks. The representative IS and illite samples taken from plutonic- and volcanic-hosted alteration zones are investigated by optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), major and trace elements and OH isotope geochemistry and KAr dating methods. Different types of hydrothermal alterations, such as propylitic and phyllic alteration in the plutonic rocks and argillic alteration in the volcanic rocks were developed as a result of intrusion of Kösedağ Pluton (syenite) into Karataş Volcanics (basaltic trachy-andesite and trachyte) with relations of hot-hot contact. The main phyllosilicate/clay minerals are characterized by kaolinite and IS in volcanic-hosted argillic alteration zones, whereas IS and illite in plutonic-hosted phyllic zones. The ordering types (Reichweite) of IS and illites are represented by R1 IS (I = 65–80 % in IS) + R3 IS (I = 90 % in IS) in the volcanic-hosted rocks, and R3 IS (I = 90 % in IS) and illite (S = 3–5 %). Dioctahedral (d060 ≤ 1.500 Å) R3 IS and illites have 1 Md + 1 M and 1 Md + 1 M + 2 M1 polytypes, respectively. The major and trace elements such as TiO2, Fe2O3, MgO, Na2O, P2O5, Sc, V, Cu, Ge, Sr, Hf, Zr and Y increase in the volcanic-hosted IS, whereas SiO2, Al2O3, K2O, Pb, W, Mo, As, Sb, Rb and U in the plutonic-hosted IS and illites. The chondrite-normalized distributions of IS and illites present a great similarity to those of host rocks. The chondrite-normalized rare earth element (REE) concentrations are more enriched in the volcanic-hosted IS in comparison with the plutonic-hosted IS and illites having distinctive Eu negative anomaly, which indicate deriving from volcanic matrix and K-feldspar, respectively. Oxygen and hydrogen isotope data of illitic clays indicate that the hydrothermal fluids are originated from magmatic water. According to stable isotopes and fluid inclusion data, IS and illites were formed at the temperature conditions ~150 °C in volcanic-hosted argillic zone, whereas ~250 °C in plutonic-hosted phyllic zones. KAr dating of alunite, IS and illite minerals indicate that the hydrothermal alteration was started at 40.45 ± 1.28 Ma, almost 2 Ma after the Q-syenite intrusion, within the plutonic body as phyllic alteration stage, and continued up to 35.27 ± 2.81 Ma, with a duration of ~5 Ma, and finalized before the exhumation of the Kösedağ Pluton (28–30 Ma). The geochemical characteristics of IS and illites were controlled by host-rock, condition, origin, and ages of alterations and they can be used as an important tool for magmatic-hydrothermal systems.

Integrated approach to understand the multiple natural and anthropogenic stresses on intensively irrigated coastal aquifer in the Mediterranean region

Understanding the major factors influencing groundwater chemistry and its evolution in irrigation areas is crucial for efficient irrigation management. Major ions and isotopes (δD-H2O together with δ18O–H2O) were used to identify the natural and anthropogenic factors contributing to groundwater salinization in the shallow aquifer of the Wadi Guenniche Plain (WGP) in the Mediterranean region of Tunisia. A comprehensive geochemical investigation of groundwater was conducted during both the low irrigation season (L-IR) and the high irrigation season (H-IR). The results show that the variation range and average concentrations of almost all the ions in both the L-IR and H-IR seasons are high. The groundwater in both seasons is characterized by high electrical conductivity and CaMgCl/SO4 and NaCl types. The dissolution of halite and gypsum, the precipitation of calcite and dolomite, and Na–Ca exchange are the main chemical reactions in the geochemical evolution of groundwater in the Wadi Guenniche Shallow Aquifer (WGSA). Stable isotopes of hydrogen and oxygen (δ18O–H2O and δD-H2O) indicate that groundwater in WGSA originated from local precipitation. In the H-IR season, the δ18O–H2O and δD-H2O values indicate that the groundwater experienced noticeable evaporation. The enriched isotopic signatures reveal that the WGSA's groundwater was influenced by irrigation return flow and seawater intrusion. The proportions of mixing with seawater were found to vary between 0.12% and 5.95%, and between 0.13% and 8.42% during the L-IR and H-IR seasons, respectively. Irrigation return flow and the associated evaporation increase the dissolved solids content in groundwater during the irrigation season. The long-term human activities (fertilization, irrigation, and septic waste infiltration) are the main drives of the high nitrate-N concentrations in groundwater. In coastal irrigation areas suffering from water scarcity, these results can help planners and policy makers understand the complexities of groundwater salinization to enable more sustainable management and development.

Paleoclimate changes across the Cenomanian–Santonian transition at the southern Neo-Tethys margin (SW Iran): An integrated approach

The Cenomanian–Santonian (C–S) carbonate successions include valuable petroleum reservoirs in the Zagros Basin. They also provide important information on the paleogeographic setting, paleoclimatic conditions, and tectonic evolution of the southern Neo-Tethys margin. This study focuses on the paleoclimatic changes across the C–S transition using the petrographical, petrophysical, paleontological, major and trace element and isotope geochemical data from three subsurface sections selected from the southern Dezful Embayment and northwestern part of the Persian Gulf. Remarkable differences in allochemical (skeletal and non-skeletal) elements indicate dissimilar paleoclimatic conditions during the Cenomanian–Turonian and Santonian. Paleoexposure events are related to diagenetic processes such as extensive meteoric dissolution (karstification) and the development of bauxitic–lateritic paleosols with high Fe, Al, and kaolinite concentrations indicating warm and humid (tropical) conditions. Increased values of Fe, Al, Rb, and 87Sr/86Sr isotopic ratios and depletion of Ca, Sr, δ18O, and δ13C considered together indicate meteoric diagenetic effects under this paleoclimatic condition. Spectral gamma measurements are used to investigate paleoclimatic conditions. Low content of Uranium (U) throughout the transgressive systems tract (TST) and high concentration in the regressive systems tract (RST) along with low contents of kaolinite within the Santonian sequence denote the predominance of arid conditions. The major fall in U concentrations at the Cenomanian–Turonian interface (CT-Exposure Surface) could be regarded as an outcome of the fall in the relative sea-level and a proxy of oxidizing conditions (Th/U > 7) that could be the consequence of a change in paleoclimate from humid/semi-humid to humid. Evidence for a 3–4 °C decrease in paleo-temperature and increase in aridity are recorded during the Cenomanian–Santonian transition in the Zagros Basin, which is in close agreement with global trends. This cooling pattern is attributed to a decline in atmospheric CO2 levels and alterations in oceanic circulation, specifically an increase in meridional circulation.

Resolved resonance region evaluations of n+ 206,207,208Pb for fast spectrum applications

Resolved resonance region evaluations of the major isotopes of natural lead, 206Pb, 207Pb, 208Pb, have been performed to support the development of Generation IV reactors. Validation of nuclear data for lead fast reactors was performed with simulations of shielding benchmarks, integral critical benchmarks, and quasi-differential scattering measurements. Sensitivity analyses of these systems showed that elastic scattering reactions above 100 keV were the dominant reactions driving system performance. The resolved resonance regions (RRRs) of the lead isotopes extend past 100 keV, making the RRR an ideal starting point to evaluate lead cross sections. Since the R-matrix requires knowledge of bound, distant, and observed resonances, it was necessary to evaluate from 10−5eV up to the respective limit of the RRR. The 208Pb RRR evaluation was extended to 1.5 MeV in order to obtain resonance parameters used to calculate new elastic scattering angular distributions up to 1.5 MeV. Resonance parameter uncertainties and covariance were generated using the R-matrix code SAMMY. The new RRR parameters show a direct improvement to the scattering kernel below 1.5 MeV which in turn greatly improves fast critical experiments over ENDF/B-VIII.0.

Using major ions and stable isotopes to improve conceptualisation of a spring-aquifer system in the Galilee Basin, Australia

Developing conceptual models is a critical step in hydrogeological studies that should utilise multiple lines of evidence and data types to minimise conceptual uncertainty, particularly in data-sparse systems. This study used new and existing major ion and isotope (O, H, Sr, C) data sets to refine a previous hydraulic-head-based conceptual model of the Galilee Basin (Australia). The analyses provide evidence for the locations of recharge and discharge areas and determine hydrochemical processes along flow paths to improve understanding of potential source waters to the Doongmabulla Springs Complex (DSC) and to infer mixing within, or exchange between aquifer units. There was good agreement between previously inferred recharge and discharge areas defined using hydraulic head data and interpretations from hydrochemical evolution along groundwater flow pathways, at least where data were available. Major ion and isotope data suggest that the DSC likely receives water from both a relatively shallow, local flow path and a deeper regional flow path. This observation is relevant to previous concerns about threats to the DSC, as mine-induced drawdown may impact the relative contributions to spring discharge from different recharge sources and aquifers. Silicate weathering in the deeper Clematis Formation and Dunda Beds, and evapotranspiration in the overlying Moolayember Formation have strong control on the total dissolved solids content. These findings suggest that the Clematis Formation and Dunda Beds are hydrochemically distinct from the Moolayember Formation, with limited exchange between these aquifers, which has important implications for model conceptualisation and ongoing monitoring of mining activities in the Galilee Basin.

Geochemical evolution of geothermal waters in the Pearl River Delta region, South China: Insights from water chemistry and isotope geochemistry

The Pearl River Delta (PRD) region in South China is abundant of geothermal water resources whereas geochemical evolution of the geothermal water is still poorly understood. In this study, geothermal water is sampled to investigate the provenance of CO2 and sulphate, residence time, recharge elevation, circulation depth, and water-interaction processes by analyzing chemistry of major ions and isotope geochemistry. The range of δ13C and content of bicarbonate reveal multiple sources of soil CO2, carbonate rocks, and small amounts of mantle CO2. The δ34S ratio and sulphate concentration are attributed to evaporites dissolution, input of atmospheric sulphur, seawater intrusion, and oxidation of pyrite. The residence time of up to 21.01 ka for geothermal water likely suggests the earliest precipitation recharge during the Late Pleistocene. Mountains or/and hills at an altitude of 300–760 m in north PRD region are currently the major recharge areas for the geothermal water which can circulate at the depths of up to 3000–4800 m along regional structures. The isotopic and hydrochemical analysis confirms that extensive water interaction with silicate rock, carbonate rock and evaporite, evaporation-crystallization process, and cation exchange are the key mechanisms that control the geochemical evolution of geothermal water in the PRD geothermal system.

Stable isotopes and hydrogeochemical evolutions of groundwater from a typical seismic fault zone in the Mt. Lushan region, Eastern China

We analyzed the major chemical components, hydrogen (δD) and oxygen isotopes (δ18O), and tritium activity in groundwater from Jiujiang well number 2 (JJ2) as well as atmospheric precipitation and water from the Maweishui spring and Tianhuajing reservoir in the Mt. Lushan region, Eastern China. The results show that the water in JJ2 is of the HCO3-Ca·Mg type, with ionic components mainly arising from calcite and dolomite mineral dissolution. According to the δD and δ18O data, the groundwater of JJ2 mainly comes from atmospheric precipitation, and the recharge elevation is 554 m. Results for tritium activity indicate that JJ2 is fed by both an ancient water supply and a new water supply within a period of 10 years. These results demonstrate that JJ2 has characteristics of both shallow and deep circulating water, which implies that aquifers involving two different recharge sources rise to the well surface via different circulation paths. That is exactly why JJ2 is tectonically sensitive and could display a remarkable gas radon anomaly before the Ruichang-Yangxin ML 5.0 earthquake in 2011. Our results also indicate that ascertaining the hydrological characteristics and cycling process of groundwater are crucial for understanding the earthquake anomalies and judging whether a seismic groundwater monitoring well is reliable or not.

Changes in geochemical and isotopic contents in groundwater before seismic events in Ischia Island (Italy)

We analysed the hydrogeochemical and isotopic contents in groundwater for the period 2002–2020, in the Ischia Island, a volcanic island in Southern Italy, and compared them with seismic events that occurred in the same period. The study is based on a large hydrochemical database, which includes chemical (major and minor compounds, metals and trace elements) and isotopic analyses (δ18O and δ2H). For each of the 34 seismic events occurred in the studied period, we considered coordinates, date, time, depth and magnitude. To exclude the influence of meteorological variability on the hydrochemistry, we examined rainfall time series measured in four stations located in the island. Results show hydrogeochemical anomalies for some chemical elements observed months before the seismic events. Arsenic, electrical conductivity, chromium and vanadium have been identified as potentially affected by hydrogeochemical anomalies related to the earthquakes. The variations in stable isotopes (δ2H and δ18O) in groundwater also seem associated with the earthquakes.This study aims to contribute to the individuation of components in groundwater prone to register sudden changes related to seismic events and it highlights the need of a continuous and long-term hydrogeochemical monitoring in seismic areas. Indeed, the conclusions of this study must be further confirmed by a future continuous monitoring of major compounds, trace elements and isotopes in groundwater to evaluate the effective temporal coincidence/lag with the seismic events.

Petrology and source characteristics of the Arbarastakh alkaline ultramafic carbonatite-phoscorite complex, the Aldan-Stanovoy Shield

Late Neoproterozoic Arbarastakh alkaline ultramafic carbonatite-phoscorite complex in the southern margin of the Siberian craton (Aldan-Stanovoy shield), includes carbonatites and phoscorites closely associated with pyroxenites-ijolites and ultramafic lamprophyres. Major and trace elements data, Sr, Nd and Pb isotope compositions for the Arbarastakh rocks have been obtained to characterize the sources involved in their formation, primary melt composition and to build the petrogenetic model.All rock varieties, excluding nepheline syenites, are characterized by incompatible elements enrichments, including light rare earth elements, and strong fractionation of REEs. The initial isotope ratios of the analyzed samples, calculated at 645 Ma, display limited variations: εNd from +5.9 to +6.9 and 87Sr/86Sr from 0.70225 to 0.70272, excluding nepheline syenite with εNd +5.4. The initial Pb isotope ratios for the most studied samples overlap with each other within uncertainties. They yield an age of 642 ± 5 Ma. The Nd and Sr isotope data of the Arbarastakh rocks generally fit the patterns of the other Neoproterozoic alkaline ultramafic carbonatite complexes of the southwestern and southern margins of the Siberian craton. Observed Sr, Nd and Pb isotope variations indicate mixing of the asthenosphere and the depleted mantle components.It is supposed that the primary melts for the Arbarastakh rocks were generated directly by low-degree melting of metasomatic phlogopite‑carbonate veins with apatite and Ti-oxides in garnet peridotite, which formed shortly before the onset of melting. Ultramafic lamprophyre (aillikite) is closest to the primary melt composition in terms of high #MgO, Cr and Ni. The aillikite and latter pyroxenite crystallized from primitive melt by fractionating the olivine, phlogopite and clinopyroxene dominated mineral assemblage that was free of feldspar. This fractionation forced Na-enrichment in the magmas resulted in liquid silicate‑carbonate immiscibility. Major and trace element and isotope data indicate that the nepheline syenites are unlikely to be related with other alkaline silicate rocks through fractional crystallization and could have been formed through pre-emplacement interaction with the ambient crustal materials. Emplacement of calcite carbonatites resulted in metasomatism of surrounding pyroxenites with formation of clinopyroxene-phlogopite-calcite carbonatites. Subsequent portions of Fe-P-enriched carbonatite magmas crystallized phoscorites and apatite-dolomitic carbonatites.

The in vacuo release of Ar and rare gases from minerals: 3. The degassing of He, Ne, Ar, Kr and Xe from irradiated apatite

The mechanisms of in vacuo release of Ar are investigated by bringing them into context with nine other rare gas isotopes and by studying the mineralogical modifications that occur in their host mineral. A 200 mg shard of Durango fluorapatite was step-heated after neutron irradiation. It contained radiogenic 4He from natural U decay and artificially produced major rare gas isotopes: 20Ne from F, 37Ar from Ca, 38Ar from Cl, 80Kr and 82Kr from Br, 128Xe from I, 131Xe from Ba and 134Xe from U. The 4He release rate was compared with that from an unirradiated aliquot.Helium was expected, and observed, to degas at the lowest furnace temperatures, with nearly complete exhaustion by 1300 °C. Neon followed a bimodal degassing pattern, with a peak of the release rate at 1178 °C and a higher one at 1406 °C. Argon degassing showed a similar bimodality. Krypton and xenon were both mostly released in a single, concentrated burst between 1362 and 1460 °C.The two Xe isotopes 128 and 131, produced from I and Ba, respectively, followed exactly the same degassing pattern. The crystallographic site of the target element had no control on the movement of the irradiation-produced rare gas atom.The He release from the irradiated and unirradiated aliquots gave two overlapping alignments in the Arrhenius diagram at temperatures between 450 and 1300 °C. The two slopes are indistinguishable at the 1 sigma level and yield an average activation energy of 62 ± 5 kJ/mol. In the 450–1300 °C temperature interval, all five rare gases showed parallel trends with an activation energy around 62 kJ/mol and release rate constants decreasing from He to Xe by about 4 orders of magnitude. Arrhenian trajectories for the Kr and Xe degassing rate merge and sharply steepen in the 1362 °C step, with a degassing rate in the 1406 °C step about 400 times higher than at lower temperatures and an activation energy of 1.28 MJ/mol. The high-T modes of the bimodal Ar and Ne release also merge on the same steep Arrhenius line, with release rate constants indistinguishable from those of Kr and Xe. This break in Arrhenius slope and the merger of four trajectories that were widely separated below 1300 °C indicate a major, energetically very costly event between 1300 and 1362 °C.The possible structural reordering was investigated with four mineralogical techniques: Raman spectroscopy, X ray diffractometry, transmission electron microscopy, and microchemical analysis by laser induced breakdown spectroscopy. Total loss of F may have transiently modified the apatite structure. Complete outgassing of Ne, Ar, Kr and Xe was only achieved after the defluorination reaction and attending displacive structural reorganization. Like in hydrated minerals, in K-feldspar, and in leucite, degassing of heavy noble gases in apatite occurs by at least two different physical mechanisms. In all of these minerals downslope extrapolation of in vacuo Ar degassing in the laboratory to temperatures of geological interest does not appear warranted.

Multiple carbon isotope excursions during the Carnian (Late Triassic) pluvial event: implications for global and regional perturbation

The Late Triassic Carnian pluvial event (CPE) was an interval marked by global climatic and environmental changes that occurred simultaneously with enhancement of the hydrological cycle. This event is characterized by multiple negative carbon isotope excursions (NCIEs). However, the driving mechanism behind these multiple NCIEs remains elusive because each of the NCIEs had different magnitudes in different geological settings. In this study, we present a high-resolution record of carbonate carbon isotope ( δ 13 C carb ) and major and trace element data from Well QZ-8 in the Qiangtang Basin, eastern Tethys. The carbon isotope profile from this well displays a similar trend to those for contemporaneous strata in the NW Tethys and South China. This trend is characterized by a distinct negative excursion during the CPE, supporting a global event. Interestingly, our results reveal five NCIEs for the first time in the marine sedimentary succession. Furthermore, each of these NCIEs corresponds well to changes in Ti/Al, Sr/Al and Sr/Ba, suggesting a regional effect of the hydrological cycle on carbon isotope excursions. This study emphasizes that each of the NCIEs was influenced by regional hydrological cycles although the long carbon isotope excursion during the CPE was driven by the global carbon cycle. Supplementary material: Tables showing major element, isotope and trace element data and element ratios, and a supplementary figure are available at https://doi.org/10.6084/m9.figshare.c.6805266

Spatial and temporal distribution of geochemical elements and their processes in different size fractions–Miri River (NW Borneo)

The toxicity, persistence, and propensity for accumulation of metals in aquatic environments have raised significant concerns globally. Expansion of urbanization with the growth of industrial and agricultural sectors in Miri City results in a high concentration of pollutants that flow directly into the Miri River. Hence, this study provides a comprehensive analysis of the Miri River water quality, focusing on spatial and temporal variations. River water samples were collected in two different time periods and analysed for physico-chemical parameters includes major ions, nutrients, metals and isotopes. Particularly, the metals were analysed in different size fractions (particulate and colloid) of the suspended solids. Geochemical plots, pollution index, geochemical modelling and factor analysis were used for the data analysis. Interpretation of data reveals that the mean concentration of metals in river water were increased from downstream to the upstream of the river irrespective of the seasons. Major ions were mostly derived from the chemical weathering of source rocks, which was supported by the Gibbs plot. Piper plot indicates the seasonal shifting of water types from Ca–Mg to Na–Cl. Isotopic signatures reveal direct atmospheric precipitation and evaporation were the major origins of river water. Fe was the dominant metal concentration in river water irrespective of the seasons (mean concentration 1.05 mg/L). Fe and Zn were the dominant metal concentration observed in all the 3 size fractions of suspended solids. Industrial activities and seawater influx dominate in the downstream, whereas weathering and agricultural inputs are significant in the upstream of the river. Particulate and colloidal fractions are the major contributors for the metal transport in the midstream and downstream of the river. The outcome of this study offer a thorough understanding of the seasonal elemental distribution at different size fractions, geochemical behaviour and the pollution status of the Miri River. With this knowledge, sustainable management strategies can be developed for this crucial water resource to the benefit of Miri community.

Major, trace element and Sr-Nd isotope evidence for a sublithospheric mantle source for the Umkondo large igneous province

The Mesoproterozoic (1.11 Ga) Umkondo large igneous province (LIP) in southern Africa and Antarctica was emplaced in < 5 Myr and is dominated by low-Ti tholeiitic doleritic-gabbroic sills. It is of particular interest because it is the least studied LIP in southern Africa with both sublithospheric and lithospheric mantle sources proposed and it coincides with the early assembly of Rodinia, so it has importance in understanding the nature of magmatism and tectonics in and around the Kalahari craton during the Mesoproterozoic. In this study, we compiled a large database of existing (∼750) and new (∼100) major and trace element data for the Umkondo province, as well as 42 new Sr-Nd isotopic measurements, to provide constraints on its magma sources and geochemical evolution. Major element compositional variations in the low-Ti tholeiites are explained by low-pressure (1 kbar) three-phase fractional crystallisation (olivine, clinopyroxene and plagioclase) of a parent magma with ∼ 10 wt.% MgO in oxidising conditions (QFM + 1). Inverse models show that the low-Ti tholeiitic magmas were derived as residual melts after the crystallization of 12%–33% olivine from primary komatiitic-basaltic magmas (up to ∼ 20 wt.% MgO) in equilibrium with mantle olivine (Fo90). Low Sm/Yb and TiO2/Yb-Nb/Yb indicate that the primary magmas were derived by 2%–20% shallow (40–50 km) partial melting of spinel lherzolite. High Sm/Yb is restricted to dyke swarms and may imply limited magma production from deeper (up to ∼ 70 km) garnet lherzolite-like sources. The low-Ti tholeiites of the Umkondo province are enriched in large ion lithophile elements (Rb-Sr-Cs-K) and depleted in high-field strength elements (Zr-Hf-Nb-Ta), indicating the involvement of crustal material and/or the subcontinental lithospheric mantle. This is supported by covariations in Th/Nb, Nb/Yb, Nb/La and Ce/Sm with generally negative ΔNb. Sr-Nd isotopes lend support to the notion that the Umkondo magmas were derived from depleted and/or enriched sublithospheric mantle sources and subsequently contaminated by enriched lithospheric material during emplacement (initial (at 1.11 Ga) 87Sr/86Sr between 0.704820 and 0.737464 and εNd between −8.9 and +5.3). The Vredefort sills are significant as they display the most depleted Sr-Nd isotopic signatures (average initial 87Sr/86Sr of 0.705342 and average εNd of 0.4) and are the least contaminated magma suite in the Umkondo province. Because of (i) the large volume of low-Ti magmas, (ii) evidence of a primary hot and MgO-rich (komatiitic) magma, and (iii) the short duration of magmatism, we suggest that the Umkondo province was formed by plume-induced melting of the sublithospheric mantle beneath the Kalahari craton in an extensional setting. This contrasts with previous suggestions that the heat source developed in response to the “thermal insulation” of the mantle beneath a thickened Kalahari craton in the absence of a mantle plume. There is further evidence from the elevated Zn/Fe that the sublithospheric mantle was lithologically heterogeneous and consisted of mixed peridotite and pyroxenite domains. There is a general lack of ultramafic cumulates in the low-Ti magma suite that may imply there was deeper ponding and storage of the primary magmas that fractionated large quantities of ultramafic rocks. There is also a paucity of high-Ti rocks in the Umkondo province that may reflect limited direct melting of the lithospheric mantle or that they are simply not as well-preserved in this province compared to the Karoo province. The similar trace element and Sr-Nd isotopic compositions of the Umkondo sills in southern Africa with the Borgmassivet sills in Antarctica support the concept that the Kalahari craton and Grunehogna terrane were adjoined at 1.11 Ga. The timing of the Umkondo province indicates there was localised lithospheric extension and upwelling asthenospheric mantle during a time of dominantly compressional tectonics on Earth at the end of the ‘boring billion’.

Role of evaporites in sodium metasomatism and formation of albite-rich rocks in IOCG provinces

Hydrothermal Iron-oxide-Cu-Au (IOCG) deposits are important exploration targets for a number of metals of economic importance. Voluminous sodium metasomatism is ubiquitous in most IOCG provinces. The origin of the metasomatic fluid responsible for the formation of albite-rich rocks in such terranes is contentious; both evaporite-derived fluid and magmatic fluid have been advocated. The Singhbhum IOCG province in India is known for hosting several polymetallic deposits from which U, Cu, and apatite-magnetite are mined as principal commodities together with Ni, Au, Ag, Se, Te, Mo, and low-Ti magnetite as by-products. Voluminous albite-rich rocks occur at several sites along the mineralized belt. Metasomatic albite schist comprising predominantly albite and quartz at Pathargora contains tourmaline intricately associated with albite. Based on textures and mineralogical associations, tourmaline is classified as: tur1: coarse nodular tourmaline ± albite ± magnetite aggregate; tur2: disseminated fine-grained tourmaline in a schistose matrix; and tur3: tourmaline + biotite + magnetite + apatite clots. All tourmaline belongs to the alkali group and most to the dravite sub-group. Very low concentrations of Li (avg 3.8 ppm), Zn (avg 6 ppm) and Mn (avg 21 ppm) but high V (avg 2130 ppm) and Ni (avg 306.5 ppm) in tur1 core (tur1c) co-genetic with albite contrast with what is reported in magmatic/magmatic-hydrothermal tourmaline of granitic affinity. The δ11B values of tourmaline are mostly positive, ranging between –4.0 and 9.2 ‰ (avg 4.0 ± 3.0; n = 79); values of tur1 cores are 4.9–9.2 ‰. Previous fluid inclusion studies described the presence of halite and barite daughter crystals in primary fluid inclusions and demonstrated the involvement of a high-temperature (≥450 °C) and high-salinity (≥50 wt% NaCl equivalent) brine in the formation of cores of tur1. Calculated δ11B values of the hydrothermal fluid in equilibrium with tur1c range from 7.3 to 11.5 ‰ (for a crystallization temperature of 450 °C). Based on the textural setting of the tur1c-albite assemblage, geochemical and boron isotope composition of tur1c, and evidence of a high saline brine, we propose that the albite schist is the product of Na-metasomatism by brines that derived major constituents from the dissolution of marine evaporite. The inferred paleo-latitude and geological environment of sedimentation related to the host lithologies are consistent with the evaporitic model. We further suggest that a similar mechanism might have played an important role in the formation of albite-rich rocks in other IOCG provinces where the involvement of evaporite-derived fluids in mineralization/alteration have been demonstrated. Similar major element, trace element and positive boron isotope (1.5–6.3 ‰) composition of tur3 suggest similar source of fluid as that of tur1c, and tur3 formed either during the same alteration event or during a separate fluid pulse. On the other hand, the mode of occurrence, very low trace element concentration and weakly negative to positive δ11B (−4 to 2.3 ‰) value of tur2 suggest their metamorphic origin.