Isotopic Compositions Of Fluids Research Articles

Cycling of fluid-mobile elements through the forearc: Insights from the Cl, B, and Li isotope composition of Costa Rican spring fluids

Loss of slab-derived volatile and fluid-mobile elements (FME) through the forearc may represent a large, unaccounted for flux out of convergent margins. To address volatile recycling through the forearc and potential changes in fluid source from the progressively dehydrating subducting slab, we collected water samples from 44 different cold and thermal (>40 °C) springs on a transect across the outer forearc (∼20–40 km to the subducting slab), forearc (∼40–80 km to the slab), and arc (∼80–120 km to the slab) in Costa Rica. We focused on the heavy halogens (Cl, Br, I), as well as B and Li, given their high fluid mobility and thus limited potential for modification by subsequent fluid-rock interaction. Chlorine, boron, and lithium stable isotope ratios show dramatic ranges from −1.7 to +1.0 ‰ (n = 43), −12.0 to +30.9 ‰ (n = 35), and −2.4 to + 27.5 ‰ (n = 38), respectively, with distinct changes across the transect consistent with a sedimentary pore fluid component in the outer forearc, fluids sourced from dehydration of the slab (sediment and altered oceanic crust) in the forearc, and minimal slab input near the arc. Variations in elemental ratios (Br/Cl, I/Cl, B/Cl, Li/B) across the transect are also largely consistent with evolving FME sources during subduction. Boron isotope ratios in some higher-temperature fluids are modified due to phase separation, whereas, lithium and chlorine isotope ratios are minimally modified. Springs located in the outer forearc along a major fault (Falla Morote) deviate from the consistent across-arc trend and record almost the full range of observed isotopic values. This extreme range in values along the fault likely represents a combination of adsorption/desorption effects, weathering, and mixing with crustal fluids. Mass balance calculations show that up to ∼ 70 % of Cl, ∼50 % of Br, ∼30 % of B, ∼15 % of I, and minimal Li may be recycled through the outer forearc and forearc springs of the Costa Rican margin, therefore fluid emission via springs in global forearc regions are a potentially significant output for FME at convergent margins.

Authigenic quartz reveals the triple oxygen isotope composition and diagenetic temperature of saline brines

Triple oxygen isotope compositions of authigenic minerals are an emerging tool for the reconstruction of fluid temperatures and the fluid isotopic composition. In this study, we analyzed euhedral authigenic quartz crystals from a halite deposit of the Upper Permian Zechstein evaporitic basin for their triple oxygen isotope composition using laser fluorination isotope ratio mass spectrometry. In the triple oxygen isotope space, additional information, such as the triple oxygen isotope composition of the ambient water, provides insights into equilibrium conditions during quartz formation that cannot be identified from δ18O alone. The triple oxygen isotope composition of authigenic quartz shows, that single oxygen isotope (δ18O) thermometry is not applicable for samples from evaporitic environments, where the fluids' δ18O deviates from dynamic oxygen isotope equilibrium. By combining the Craig and Gordon evaporation model with H2O – SiO2 triple oxygen isotope equilibrium fractionation, we reconstruct the formation temperature of authigenic quartz and the triple oxygen isotope composition of the marine-derived saline brine pore fluid in equilibrium with the quartz. We obtain temperatures of 90 to 130 °C that is interpreted as crystallization temperatures of microcrystalline quartz in pore fluid of halite during burial diagenesis. The triple oxygen isotope composition of authigenic quartz from evaporitic environments is suited as a geochemical tracer for fluid oxygen isotope compositions and ancient fluid or diagenetic temperatures.

Determination of water balance maintenance in Orcinus orca and Tursiops truncatus using oxygen isotopes.

The secondary adaptation of Cetacea to a fully marine lifestyle raises the question of their ability to maintain their water balance in a hyperosmotic environment. Cetacea have access to four potential sources of water: surrounding salt oceanic water, dietary free water, metabolic water and inhaled water vapour to a lesser degree. Here, we measured the 18O/16O oxygen isotope ratio of blood plasma from 13 specimens belonging to two species of Cetacea raised under human care (four killer whales Orcinus orca, nine common bottlenose dolphins Tursiops truncatus) to investigate and quantify the contribution of preformed water (dietary free water, surrounding salt oceanic water) and metabolic water to Cetacea body water using a box-modelling approach. The oxygen isotope composition of Cetacea blood plasma indicates that dietary free water and metabolic water contribute to more than 90% of the total water input in weight for cetaceans, with the remaining 10% consisting of inhaled water vapour and surrounding water accidentally ingested or absorbed through the skin. Moreover, the contribution of metabolic water appears to be more important in organisms with a more lipid-rich diet. Beyond these physiological and conservation biology implications, this study opens up questions that need to be addressed, such as the applicability of the oxygen isotope composition of cetacean body fluids and skeletal elements as an environmental proxy of the oxygen isotope composition of present and past marine waters.

Stable Isotope (δ18O, δD) Composition of Magmatic Fluids Exsolved from an Active Alkaline Magma Chamber—The Case of the AD 79 Magma Chamber of Vesuvius

Stable Isotope (δ18O, δD) Composition of Magmatic Fluids Exsolved from an Active Alkaline Magma Chamber—The Case of the AD 79 Magma Chamber of Vesuvius

Triple oxygen isotopes in intertrappean fossil woods: Evidence of higher tropical rainfall during Deccan volcanism

Despite several attempts, the effects of volcanism and greenhouse gas emission on climate (e.g., rainfall) over India across the Cretaceous/Palaeogene Boundary (66.1 ± 0.01 Ma) remain a contentious issue. Inferences from conventional isotopic, palaeosol, floral analysis, and palaeoclimate models are contradictory ranging from much lower- to higher-than-today rainfall during this high CO2 atmosphere. To resolve this, robust tracer of triple oxygen isotopic ratios (ẟ18O-∆′17O) of silicified fossil woods from Deccan intertrappean lacustrine sediments, central India were analysed for retrieving the silicification temperature and ambient fluid (water) isotopic composition. Under certain assumptions and uncertainty, triple oxygen isotope data indicate that the fluids were derived from a mixture of meteoric and hydrothermal water. The meteoric water end member possibly had a low ẟ18OVSMOW value (∼− 12 ± 2‰) compared to the modern mean monsoon rainwater (∼− 5‰) which implies a substantially higher rainfall than today (∼1760 ± 200 to 1860 ± 200 mm/year) in the terminal Cretaceous India. This result supports the prediction of elevated precipitation by the recent new generation of global coupled models that consider various feedbacks and ocean dynamics, at a high CO2 atmosphere. It is also consistent with the paleo-botanical evidence but far exceeds the amount predicted by the older paleoclimate models pertaining to the Cretaceous period.

Applicability of carbonate clumped isotope thermometry in the Tuchang-Jentse geothermal field

Temperature and oxygen isotope composition of fluids, which are critical for reconstructing thermal structures and characterizing hydrothermal fluids in a geothermal system, can be obtained using carbonate clumped isotope analysis. Ideally, carbonate clumped isotope compositions (Δ47) recording the thermal fluid temperatures and compositions for fault-associated veins and rhombic calcite crystals inside open cracks demonstrate previous tectonic activities and present reservoir conditions, respectively. We studied the clumped isotope geochemistry of veins and travertines in outcrops and cuttings from exploration wells in the Tuchang–Jentse geothermal field in Taiwan. The Δ47-based temperatures (Δ47-T; 161−8+8 to 238−14+16 °C) and calculated δ18Ofluid values (+2.0 to +5.0‰) of vein calcites were the highest, indicating mixing of the magmatic/metamorphic fluids with the meteoric water after water–rock interaction in the deep thermal fluid cycle and migration to shallow areas by fault activity. Rhombic calcites with high Δ47-T (142−6+6 to 185−4+5 °C) and low calculated δ18Ofluid (−9.1 to −5.3‰) correspond to downhole temperatures and measured δ18Ofluid of thermal fluids in the exploration wells, respectively, suggesting that the latest thermal fluid was of meteoric water origin. Travertines near faults have low calculated δ18Ofluid (−8.9 to −1.0‰) and Δ47-T that are above air temperatures (32−9+9 to 95−9+10 °C), implying that the local groundwater was subsequently heated by or mixed with deep fluid. Carbonate clumped isotope thermometry application demonstrates that the carbonate clumped isotope thermometer not only precisely estimates temperature in the carbonate-dominated system using drill cutting samples during the exploration phase, but also reveals the spatial and temporary evolution of geothermal fluids used as a reference for future site selection planning.

S, Pb, and Fe isotope compositions of sulfides in middle and southern Okinawa Trough: Implying the complicated hydrothermal systems in back-arc spreading centers

Sulfur, lead, and iron isotopic systematics of sulfides from the Iheya North hydrothermal field in middle Okinawa Trough and the Yonaguni Knoll IV hydrothermal field in southern Okinawa Trough were investigated to understand the origin of ore-forming material and isotope fractionation during sulfide precipitation in back-arc spreading centers. The δ34S values (from 8.60‰ to 9.68‰) of sulfide minerals in Iheya North field suggest sulfur was derived from the leaching of basement rocks and the reduction of seawater sulfate. But an additional light sulfur source from the dissolution of biogenic sulfides in sediments is indispensable for the observed low δ34S values (between 4.78‰ and 4.97‰) of Yonaguni Knoll IV sulfides. Lead isotope compositions of all sulfides vary in a relatively wide range (206Pb/204Pb = 18.432 to 18.563, 207Pb/204Pb = 15.579 to 15.671, and 208Pb/204Pb = 38.539 to 38.979, respectively) which involves the mixing of mantle-derived and sediment-derived lead in varying proportions. Unusually high radiogenic lead isotope ratios of Yonaguni Knoll IV sulfides (207Pb/204Pb = 15.628 to 15.671, and 208Pb/204Pb = 38.854 to 38.979) imply the presence of old crustal fragments beneath southern OT. The hydrothermal fluids in OT are characterized by extremely low calculated δ56Fe values (−1.00‰ to −1.32‰) which is attributed to reducing sediments. The paired Fe-isotope compositions of pyrite and chalcopyrite revealed significantly different iron isotope compositions of hydrothermal fluids in study areas and extremely complicated ore-forming processes. Rapid precipitation of pyrite from FeS precursors accompanying iron isotopic disequilibrium moves from FeS-fluid equilibrium to pyrite-fluid equilibrium during pyrite recrystallization. The combination of sulfur, lead, and iron isotopic data suggests that hydrothermal systems in back-arc spreading centers related to plate subduction are generally affected by mantle, overlying sediments as well as potential old continental crust fragments, which results in various hydrothermal fluids and complicated mineralization processes.

Structural geology of the Cadillac Group along the Malartic segment of the Larder Lake Cadillac deformation zone, Quebec, and implications for gold mineralization

The gold-endowed Larder Lake Cadillac deformation zone (LLCDZ) in the Abitibi greenstone belt of the Archean Superior Province generally trends east but swings to the southeast along the Malartic segment in Quebec. Immediately north of the LLCDZ along this segment, deformation of the less than ca. 2687 Ma metasedimentary Cadillac Group began with the formation of isoclinal F1 folds, which are overprinted by post-2676 ± 2.0 Ma regional F2 folds with an axial planar S2 cleavage oriented parallel to the trend of the Malartic segment. Auriferous quartz veins strike east–west (085°) anticlockwise to bedding and S2. They are folded into sigmoidal S-shaped folds due to sinistral shear parallel to bedding. Later dextral shearing segmented the veins and folded the F2 folds into Z-shaped F3 folds. The veins are similar in structural chronology, fluid isotopic composition (calculated [Formula: see text] value between –9.5‰ and –3.4‰ and [Formula: see text] values of 12‰), and isotopic re-equilibration temperatures (469 and 498 °C, quartz–biotite oxygen thermometer) to the veins at the nearby Canadian Malartic deposit to the east. They possess comparable Au–As–Sb association and sericite-arsenopyrite alteration halo, as other Cadillac-Group-hosted veins at the Lapa mine to the west. Collectively, they constitute a vein field that extends across the entire length of the Malartic segment. Contrary to recent interpretations of the Malartic segment as an early accretionary structure that controlled the emplacement of gold deposits, its southeast trend is interpreted as the short limb of a broad Z-shaped flexure that formed during later F3 folding of the LLCDZ.

Intensified microbial sulfate reduction in the deep Dead Sea during the early Holocene Mediterranean sapropel 1 deposition.

The hypersaline Dead Sea and its sediments are natural laboratories for studying extremophile microorganism habitat response to environmental change. In modern times, increased freshwater runoff to the lake surface waters resulted in stratification and dilution of the upper water column followed by microbial blooms. However, whether these events facilitated a microbial response in the deep lake and sediments is obscure. Here we investigate archived evidence of microbial processes and changing regional hydroclimate conditions by reconstructing deep Dead Sea chemical compositions from pore fluid major ion concentration and stable S, O, and C isotopes, together with lipid biomarkers preserved in the hypersaline deep Dead Sea ICDP‐drilled core sediments dating to the early Holocene (ca. 10,000 years BP). Following a significant negative lake water balance resulting in salt layer deposits at the start of the Holocene, there was a general period of positive net water balance at 9500–8300 years BP. The pore fluid isotopic composition of sulfate exhibit evidence of intensified microbial sulfate reduction, where both δ34S and δ18O of sulfate show a sharp increase from estimated base values of 15.0‰ and 13.9‰ to 40.2‰ and 20.4‰, respectively, and a δ34S vs. δ18O slope of 0.26. The presence of the n‐C17 alkane biomarker in the sediments suggests an increase of cyanobacteria or phytoplankton contribution to the bulk organic matter that reached the deepest parts of the Dead Sea. Although hydrologically disconnected, both the Mediterranean Sea and the Dead Sea microbial ecosystems responded to increased freshwater runoff during the early Holocene, with the former depositing the organic‐rich sapropel 1 layer due to anoxic water column conditions. In the Dead Sea prolonged positive net water balance facilitated primary production and algal blooms in the upper waters and intensified microbial sulfate reduction in the hypolimnion and/or at the sediment–brine interface.

Thallium isotope compositions of subduction-zone fluids: Insights from ultra-high pressure eclogites and veins in the Dabie terrane, eastern China

Dehydration of the subducted slab is a crucial process in the generation of arc magmas. However, the mineralogical controls of slab dehydration remain uncertain. Thallium (Tl) isotopes have emerged as tracers of subducted slab components, but the Tl isotope characteristics of slab fluids are not known. High-pressure metamorphic veins and host eclogites in the Dabie terrane (China) provide important information on the composition and evolution of subduction zone fluids. In this study, we present the first Tl concentration and Tl isotope data for two high-pressure metamorphic epidote-rich veins formed through breakdown of lawsonite, as well as host eclogites and phengite separates, from the Ganghe and Hualiangting areas. The high Tl concentrations in phengite separates and identical Tl isotope compositions between phengites and their host bulk eclogites demonstrate that phengite controls the overall inventory of Tl in the host eclogites. Generally, the vein samples from both areas have much lower Tl concentrations than their host eclogites, suggesting that the fluids from which the veins precipitated were derived from phengite-bearing eclogites that retained Tl in the residue. The Ganghe eclogites display similar Tl isotope compositions compared with Ganghe omphacite-epidote vein. This similarity indicates that the vein-forming fluid was likely derived from the host eclogites, and that Tl isotopes did not fractionate during fluid-release. Three generations of veins in the Hualiangting area record variable Tl isotope values and were likely derived from multi-stage dehydration of heterogeneous host eclogites, some of which may have contained a sediment component. We argue that fluids derived from eclogite dehydration are likely characterized by higher Cs/Tl ratios compared to their host eclogites. Arc magmas that display high Cs/Tl (i.e. >15) that cannot be caused by variations in slab source composition, coupled with relatively low Ba/Th ratios, are likely to directly record the presence of residual phengite at subarc depths.

Tourmaline boron isotopes trace metasomatism by serpentinite-derived fluid in continental subduction zone

Subduction of low-density continental crust to subarc depths is generally associated with preceding subduction of the oceanic slab. However, the original oceanic signature is often overprinted by subsequent fluid metasomatism from the subducting continental crust. As a result, it is generally difficult to trace the geochemical processes of previous oceanic subduction in collisional orogens. This issue can be potentially resolved by applying B isotopes to metamorphic rocks from continental subduction zones. Here a combined study of whole-rock geochemistry and in situ tourmaline B isotopes was carried out for coesite-bearing whiteschist and phengite schist, as well as country rock metagranitoids from the Dora-Maira Massif in the Western Alps. While all these metamorphic rocks have a similar protolith of Permian granites, whiteschist and phengite schist experienced Mg-rich fluid metasomatism during the continental subduction, evidenced by their much higher MgO contents than the metagranitoids. Tourmaline in the metagranitoid (Tur-G) is schorlitic (XMg = 15–55) with low δ11B values from −13 to −6‰, and is consistent with a magmatic origin. In contrast, tourmaline in metasomatic rocks (Tur-S) is mainly dravitic with the highest XMg worldwide (XMg = 90–98) and high δ11B values of −5 to +1‰. Integrated with whole-rock geochemistry and previous studies, Tur-S is interpreted to grow during the infiltration of external fluids that were highly enriched in MgO and relatively enriched in 11B. According to the B isotope compositions of precursor tourmalines, it is estimated that the external fluids had significantly higher δ11B values than +2.4‰. Based on B isotope compositions of both Tur-S and metasomatic fluids, our quantitative modeling suggests that the metasomatic fluids most likely originated from the mantle wedge serpentinite that was formed during the preceding oceanic subduction stage. Therefore, tourmaline B isotopes in the ultrahigh pressure metamorphic continental crust can be used to trace preceding fluid metasomatism at the interface between oceanic slab and mantle wedge. The mantle wedge serpentinite plays an important role in modifying the geochemical composition of deeply subducted supracrustal rocks and probably also the mantle sources of arc magmas.

In situ multiple sulfur isotopes and chemistry of pyrite support a sedimentary source-rock model for the Linwang Carlin-type gold deposit in the Youjiang basin, southwest China

The Linwang gold deposit is a representative example of Carlin-type gold deposits in Youjiang basin, southwest China. High-grade ores are hosted in silicified and brecciated siltstone, sandstone, and mudstone of the Middle Triassic and are controlled by high-angle reverse faults. Optical microscopy pyrite texture, in situ laser ablation-inductively coupled mass spectrometry (LA-ICP-MS) trace elements, and secondary ion mass spectrometry (SIMS) multiple sulfur isotopes analyses are used to examine the different types of pyrites to constrain the sources of reduced sulfur and metals for the Linwang deposit.Petrography and pyrite chemistry studies distinguished three generations of pyrite: Pre-ore pyrite (Py 1) and ore pyrites (Py 2 and Py3). Pre-ore pyrite is framboidal, anhedral to euhedral pyrite with highest concentrations of Co, Ni, and Pb and is interpreted to have a sedimentary (diagenetic) origin. Ore pyrites were formed by hydrothermal fluids via sulfidation of Fe-bearing minerals in the host rocks. They commonly rimed and partially replaced the pre-ore pyrite and have an As-rich inner rim (Py 2) and an Au-rich outer rim (Py 3) with lowest contents of Co, Ni, and Pb. All pyrites contain Au, As, Sb, Cu, Tl, and Se, with increasing concentrations from Py 1 to Py 3.In situ SIMS multiple S isotope analyses show that all pyrites in the Linwang deposit have narrow ranges of δ34S values, with average of +5.13‰ for Py 1, +4.84‰ for Py 2, and +4.53‰ for Py 3, and near zero of Δ33S values (−0.02‰ to +0.03‰), suggesting that the S within the Linwang deposit was most likely sourced from the Triassic sedimentary rocks that host the deposit. A near zero Δ33S signature in all pyrites indicates no record of the assimilation of Archean sulfur, implying the deep basement of Archean rocks beneath the basin were not involved the formation of the Linwang deposit.Oxygen and hydrogen isotope compositions of ore fluids (δ18OH2O = +11.7‰ to +16.5‰, δD = −71‰ to −57‰) indicate a metamorphic origin. Based on these data, we propose a sedimentary source-rock model for the Linwang deposit in which the ore fluids were generated by release of previous Au-bearing sedimentary pyrites during metamorphism of sedimentary rocks. The stress relaxation of Yanshanian orogeny resulted in the ore fluids flowed upward along the fault zones into structural highs where they reacted with Fe-bearing minerals in the host rocks to deposit Au-rich pyrite. The preconcentration of Au, As, and Sb in sedimentary pyrite and gold deposition process are key to the formation of the Linwang deposit and may apply to the genesis of other Carlin-type gold deposits in the Youjiang basin.

A New Insight Into Seawater-Basalt Exchange Reactions Based on Combined δ18O—Δ′17O—87Sr/86Sr Values of Hydrothermal Fluids From the Axial Seamount Volcano, Pacific Ocean

The δ18O values of submarine vent fluids are controlled by seawater-basalt exchange reactions, temperature of exchange, and to a lesser extent, by phase separation. These variations are translated into the δ18O values of submarine hydrothermal fluids between ca. 0 and + 4‰, a range defined by pristine seawater and equilibrium with basalt. Triple oxygen isotope systematics of submarine fluids remains underexplored. Knowing how δ17O and δ18O change simultaneously during seawater-basalt reaction has a potential to improve i) our understanding of sub-seafloor processes and ii) the rock-based reconstructions of ancient seawater. In this paper, we introduce the first combined δ17O-δ18O-87Sr/86Sr dataset measured in fluids collected from several high-temperature smoker- and anhydrite-type vent sites at the Axial Seamount volcano in the eastern Pacific Ocean. This dataset is supplemented by measurements of major, trace element concentrations and pH indicating that the fluids have reacted extensively with basalt. The salinities of these fluids range between 30 and 110% of seawater indicating that phase separation is an important process, potentially affecting their δ18O. The 87Sr/86Sr endmember values range between 0.7033 and 0.7039. The zero-Mg endmember δ18O values span from -0.9 to + 0.8‰, accompanied by the Δ′17O0.528 values ranging from around 0 to −0.04‰. However, the trajectory at individual site varies. The endmember values of fluids from focused vents exhibit moderate isotope shifts in δ′18O up to +0.8‰, and the shifts in Δ′17O are small, about −0.01‰. The diffuse anhydrite-type vent sites produce fluids that are significantly more scattered in δ′18O—Δ′17O space and cannot be explained by simple isothermal seawater-basalt reactions. To explain the observed variations and to provide constraints on more evolved fluids, we compute triple O isotope compositions of fluids using equilibrium calculations of seawater-basalt reaction, including a non-isothermal reaction that exemplifies complex alteration of oceanic crust. Using a Monte-Carlo simulation of the dual-porosity model, we show a range of possible simultaneous triple O and Sr isotope shifts experienced by seawater upon reaction with basalt. We show the possible variability of fluid values, and the causal effects that would normally be undetected with conventional δ18O measurements.

Mineralisation of atmospheric CO2 in hydromagnesite in ultramafic mine tailings – Insights from Mg isotopes

In this study we present the first Mg isotope data that record the fate of Mg during mineralisation of atmospheric CO2 in ultramafic mine tailings. At the Woodsreef Asbestos Mine, New South Wales, Australia, weathering of ultramafic mine waste sequesters significant amounts of CO2 in hydromagnesite [Mg5(CO3)4(OH)2·4H2O]. Mineralisation of CO2 in above-ground, sub-aerially stored tailings is driven by the infiltration of rainwater dissolving Mg from bedrock minerals present in the tailings. Hydromagnesite, forming on the surface of the tailings, has lower δ26Mg (δ26MgHmgs = −1.48 ± 0.02‰) than the serpentinised harzburgite bedrock (δ26MgSerpentinite = −0.10 ± 0.06‰), the bulk tailings (δ26MgBulk tailings = −0.29 ± 0.03‰) and weathered tailings containing authigenic clay minerals (δ26MgWeathered tailings = +0.28 ± 0.06‰). Dripwater (δ26MgDripwater = −1.79 ± 0.02‰) and co-existing hydromagnesite (δ26MgHmgs = −2.01 ± 0.09‰), forming in a tunnel within the tailings, and nodular bedrock magnesite [MgCO3] (δ26MgMgs = −3.26 ± 0.10‰) have lower δ26Mg than surficial fluid (δ26Mg = −0.36‰) and hydromagnesite.Complete dissolution of source minerals, or formation of Mg-poor products during weathering, is expected to transfer Mg into solution without significant alteration of the Mg isotopic composition. Aqueous geochemical data and modelling of saturation indices, along with Rayleigh distillation and mixing calculations, indicate that the 26Mg-depletion in the drip water, relative to surficial water, is the result of brucite dissolution and/or precipitation of secondary Mg-bearing silicates and cannot be assigned to bedrock magnesite dissolution. Our results show that the main mineral sources of Mg in the tailings (silicate, oxide/hydroxide and carbonate minerals) are isotopically distinct and that the Mg isotopic composition of fluids and thus of the precipitating hydromagnesite reflects both isotopic composition of source minerals and precipitation of Mg-rich secondary phases. The consistent enrichment and depletion of 26Mg in secondary silicates and carbonates, respectively, underpins the use of the presented hydromagnesite and fluid Mg isotopic compositions as a tracer of Mg sources and pathways during CO2 mineralisation in ultramafic rocks.

Fluid compositions reveal fluid nature, metal deposition mechanisms, and mineralization potential: An example at the Haobugao Zn-Pb skarn, China

AbstractFluid inclusion compositions obtained from laser ablation–inductively coupled plasma–mass spectrometry at the Haobugao Zn-Pb skarn in northeastern China provide constraints on fluid origin, evolution, and metal deposition mechanisms and an example of evaluating mineralization potential. Metal concentrations in the prograde fluids were high (up to 1.4 wt% Zn and 1.8 wt% Pb) but remained in solution, likely due to the high temperatures (440–575 °C) and salinities (35.4–45.3 wt% NaCl equivalent). Absolute concentrations of elements (e.g., Rb and Na) and mass ratios (e.g., Zn/Na and K/Na) reveal that the early, prograde fluids were magmatic, consistent with the oxygen isotope composition of fluids (δ18OH2O = 5.5‰–8.5‰). Later mixing with a meteoric fluid caused dilution and Zn-Pb deposition, as revealed by lowered element concentrations and Pb/(Na + K) and Zn/(Na + K) ratios in the sulfide-stage fluid inclusions. Elevated Ca/K ratios in sphalerite-hosted inclusions indicate fluid-carbonate reactions that buffered fluid pH, also facilitating Zn-Pb precipitation. Although cassiterite and molybdenite occur locally at Haobugao, mass balance calculation shows low metal endowment (maximum 2900 t Sn and 2200 t Mo) of the system. Furthermore, the generally unchanged Sn/(Na + K) and Mo/(Na + K) ratios from pre- to late-mineralization fluids suggest that the fluids were never saturated in Sn and Mo. Therefore, finding much Sn or Mo at Haobugao is unlikely. This demonstrates a potential tool for evaluating the metal endowment of a mineral prospect, which may guide exploration.

Fluid geochemistry of the Los Humeros geothermal field (LHGF - Puebla, Mexico): New constraints for the conceptual model

Geothermal power in Mexico is mainly produced in four geothermal fields operated by the Comision Federal de Electricidad (CFE): Cerro Prieto, Los Azufres, Los Humeros, and Las Tres Virgenes. The Los Humeros Geothermal Field (LHGF) is ranked third in terms of generated capacity, and in the last decade its installed capacity has doubled (up to 95.0 MW). Further increases in the geothermal power generation capacity in Mexico are planned, and thus the LHGF warrants further examination. The development and growth phases of any geothermal project must start from an awareness of the conceptual model of the natural system studied. The recharge mechanism, feeding zones, and fluid flow-path must be identified, along with the estimation of the temperature at the productive level and of phase separation (liquid – steam). To accomplish this, detailed fluid geochemical surveys were carried out in June 2017 and March 2018, in which 57 and 87 samples were collected, respectively, from cold and thermal springs, water wells and maar lakes located around and inside the LHGF. Samples from fumaroles inside the producing area were also collected for the first time, together with fluid from re-injection wells. The presence of a meteoric component, which plays an important role at the regional scale, is confirmed by the chemical and isotope data, and its contribution in terms of recharge may be higher than previously assumed. The Sierra Madre Oriental, on the west side of the LHGF, is characterized by widespread outcrops of limestone belonging to the same geological formation as those at the bottom of the LHGF. The isotope composition (δD and δ18O, respectively -77.3‰ and -10.50‰ for the hypothetical Infiltration Water - IW) is similar to that observed in cold springs located in the Sierra Madre Oriental, and from this the evolution of isotopes in the liquid-rock-steam system during water-rock interaction and phase separation processes can be modelled. Thus, the experimental data obtained for natural gas emissions (fumarolic condensates) and for geothermal fluids can be reproduced. These findings suggest that geothermal fluids in the LHGF are likely to be derived from meteoric water infiltrating (IW) the limestone outcrops of the Sierra Madre Oriental. During their flow-path, the infiltrating waters exchange isotopes at a high temperature with the crustal rocks, which have a much higher 18O/16O ratio, resulting in a shift towards higher δ18O (-4.35‰ ± 1) as the water O exchanges with rock O. The vapor phase can be separated from this deep water (DW) and it is discharged from the fumarolic effluents of Loma Blanca. Single Step Vapor Separation (SSVS) and Continuous Steam Separation processes (CSS) were modelled using stable isotopes of water. The results of geochemical modeling agree with available data for geothermal liquids discharged from several geothermal wells, suggesting that steam separation may be interpreted either as SSVS or CSS. Other processes can affect the chemistry and isotope composition of geothermal fluids (e.g. phase segregation, gas exchange, contributions from magmatic-volcanic deep fluids and re-injection fluids). The proposed conceptual model is consistent with both the geochemical data and the geological setting, and provides a useful point of reference for examining the fluid flow-path and geochemical processes active in the LHGF, at least at a general level.An involvement of magmatic-volcanic deep fluids in the feeding mechanism of the geothermal system cannot be excluded at priori, but the regional meteoric end-member is supported by the data and it seems the most important component.

Genesis of the Shangxu orogenic gold deposit, Bangong-Nujiang suture belt, central Tibet, China: Constraints from H, O, C, Si, He and Ar isotopes

Shangxu is an orogenic gold deposit in the Bangong-Nujiang suture zone, central Tibet, China, formed in the Early Cretaceous orogene, related to convergence and collision between the Qiangtang and Lhasa terranes. The mineralization at Shangxu is hosted by Jurassic turbidite sedimentary rocks of the Mugagangri Group, and is associated with a regional fault system. Hydrothermal minerals develop muscovite, carbonate, sulfides and chlorite. Hydrothermal fluids record three main hydrothermal stages based on mineral paragenesis. The earliest is barren quartz stage (H1), which is pre-ore. During the early mineralization quartz-pyrite stage (H2a), defined by massive quartz veins with minor euhedral pyrite and gold, hydrothermal fluids had a δ18Ofluid of 6.1–6.4‰, δD of −74 to −116‰, δ13CCO2 of −5.4 to −7.6‰, and δ30Si of −0.1‰. In the quartz-pyrite-sulfides stage (H2b), characterized by abundant quartz, granular pyrite, muscovite with minor chalcopyrite, galena, sphalerite and gold, fluids had a δ18Ofluid of 7–8.2‰, δD of −109 to −120‰, δ13CCO2 of −9.6‰ and δ30Si of −0.1 to −0.2‰. During the ankerite-sulfide stage (H3a), distinguished by abundant ankerite, muscovite, sulfides with minor quartz and chlorite, hydrothermal system had a fluid with δ18Ofluid of 4.9–5.3‰, δD of −125.3‰, δ30Si of −0.1‰, δ13CCO2 of −12.4‰ in quartz inclusion fluid and δ13CCO2 of −2.7‰ in ankerite. The calcite-sulfide stage (H3b) is characterized by calcite, sulfides, with minor quartz and chlorite. Quartz formed earlier than calcite from a fluid having a δ18Ofluid of 6.4‰, δD of −112.6‰, δ30Si of −0.1‰, and δ13CCO2 of −7.4‰, after which calcite precipitated from a hydrothermal fluid with δ18Ofluid of 5.5–9‰, δ13CCO2 of −0.5 to −2.8‰. Hydrothermal fluids in H2b pyrite have 3He/4He ratios of 0.27–0.42Ra and 40Ar/36Ar ratios of 313–372.The stable isotope composition of hydrothermal fluids from the Shangxu gold deposit is similar to that of typical orogenic gold deposits. The early stage (H1), methane-bearing fluids were probably sourced from the basin sediments, leading to precipitation of early barren quartz veins and siderite alteration. From the quartz-sulfide stage (H2) to carbonate-sulfide stage (H3), hydrothermal fluids were likely derived from dissolution of the marine carbonate cement from sedimentary host rocks during metamorphism at depth. The decreasing δD and δ13C of the ore-forming fluids from early to late suggests mixing with δ13C-depleted oxidized graphite in sedimentary rocks, meteoric waters or reation between δD-depleted organic matters. Generally, these fluids were likely generated at depth through prograde metamorphic devolatilization of hydrous minerals in the deeper equivalents of the sedimentary rocks of the Mugagangri Group. Sulfur and gold, by inference, likely originated from sedimentary/diagenetic pyrite or the metasedimentary rocks between the greenschist and amphibolite facies, and migrated with the metamorphic fluids. During transportation to the site of deposition, gold-bearing fluids variably reacted with country rocks.

Molybdenum isotope ratios in Izu arc basalts: The control of subduction zone fluids on compositional variations in arc volcanic systems

Molybdenum isotope variations in mafic arc lavas have mainly been attributed to the influence of slab-derived components, such as subducted sediment melts and aqueous fluids. The latter have been hypothesised to fractionate Mo isotopes through interaction with the oceanic crust and carry an isotopically heavy signal that is transferred to the source of arc magmas. Thus, understanding Mo isotope systematics in subduction zones requires characterising the Mo isotope composition of slab-derived fluids and their influence on the Mo isotope budget of arc magmas. However, Mo isotope data reported to date show a considerable influence from subducted sediments that complicate accurate constraints being placed on the fluid contribution. We present Mo isotope data for mafic lavas from the Izu arc, a highly depleted oceanic island arc whose magma compositions show a dominant control from slab-derived fluids. The lavas from the Izu volcanic front are isotopically heavier than MORB and the depleted mantle. Their δ98/95Mo (the relative difference in measured 98Mo/95Mo to NIST 3134) systematically varies with indicators for fluid-mobile element enrichment, suggesting that slab-derived fluids in the Izu arc have heavy Mo isotope compositions. Additionally, co-variations with radiogenic 143Nd/144Nd and 176Hf/177Hf point to a relationship between the addition of aqueous fluids and compositional heterogeneity of the sub-arc mantle. We present mass balance models that show that the influence of subduction zone fluids on the trace element pattern of arc magmas is more dominant when these are added to a more depleted and refractory sub-arc mantle, which preferentially melts due to a relatively higher fluid flux. The mass balance of Mo in the Izu arc predicts a light Mo isotope composition for the residual oceanic crust as a result of the preferential removal of isotopically heavy Mo during slab dehydration, consistent with previous suggestions for the Mariana arc and isotopically light Mo previously reported for eclogites.

Lithium isotope compositions of U.S. coals and source rocks: Potential tracer of hydrocarbons

Kerogen in organic-rich rocks contains trace amounts of lithium (Li) that has been overlooked as a contributor to the global Li geochemical cycle. This study examined a variety of coals where kerogen is concentrated (>50% organic carbon) and hydrocarbon source rocks of different ages, depositional environments and thermal maturity to determine their range of Li isotopic compositions (δ7Li‰) and factors that influence their compositions.Using Secondary Ion Mass Spectrometry (SIMS), we analyzed 22 coals and 4 hydrocarbon source rocks (Types I, II, III), to determine the δ7Li of kerogen in situ, without chemical isolation of phases that can alter their original isotopic compositions. The δ7Li values of the coals surveyed are distinctly isotopically light (<0‰) compared to most natural minerals and fluids. In immature coals, with a vitrinite reflectance in oil (VRo) of ≤0.5%, kerogen δ7Li values average –23.4 ± 1.1‰ and become heavier with increasing thermal grade to temperatures of gas generation (VRo ~1.3%). The linear correlation between δ7Li and VRo suggests that 6Li may be preferentially released to pore fluid from kerogen during thermal maturation. Notably, authigenic clays forming at diagenetic temperatures substitute Li from pore fluids into silicate layers, therefore, the Li isotopic composition of the clays may record fluid isotopic compositions influenced by organic-Li sources.NanoSIMS isotopic maps of the Lower Bakken Shale, and SIMS measurements of the Green River Shale show isotopically light Li associated with C-dominated areas, and heavier δ7Li with Si-dominated areas of the hydrocarbon source rocks. We conclude that kerogen is a source of isotopically light Li that contributes to fluids during thermal maturation and hydrocarbon generation. Kerogen may be a significant contributor of Li to pore fluids and its distinctly light Li isotopic composition relative to other terrestrial waters and minerals could provide a tracer of organic inputs to the global geochemical cycle.

Geology and genesis of the Early Paleozoic Zhengguang intermediate-sulfidation epithermal Au-Zn deposit, northeast China

Zhengguang is a partly eroded (about ≥500 m being eroded), structurally controlled intermediate sulfidation (IS) epithermal gold-zinc deposit, characterized by wide distribution of base metal sulfides, Fe-poor sphalerite and Mn-calcite, hosted by the Late Cambrian-Early Ordovician basaltic-andesitic volcanic and volcano-sedimentary rocks in northeast China. The deposit is located 4 and 8 km from the Early Ordovician Tongshan (including several IS veins about ~500 m away in the east called East Tongshan) and Duobaoshan porphyry copper deposits, respectively. A 484.8 ± 8.7 Ma (MSWD = 198) of Re-Os isochron age on pyrite indicates that it is the most ancient intermediate sulfidation deposit that has been dated.Four stages of veins have been discerned at Zhengguang. Early magnetite ± chalcopyrite ± epidote ± chlorite and K-feldspar ± pyrite ± chalcopyrite veins (stage I) were associated with restricted K-feldspar ± epidote (locally with chlorite) alteration and propylitic (epidote ± chlorite ± calcite) assemblages. Two primary epithermal gold stages developed at Zhengguang: pyrite-quartz ± Fe-poor sphalerite ± chalcopyrite ± galena ± electrum ± petzite ± hessite ± tetrahedrite/tennantite ± adularia veins (stage II) and (Mn-)calcite-quartz-pyrite ± Fe-poor sphalerite ± chalcopyrite ± galena ± hessite ± native gold (stage III), plus a late barren stage characterized by little sulfides (calcite ± chlorite ± hematite ± quartz, stage IV). Gold occurs chiefly as micro-inclusions of electrum and petzite in pyrite and sphalerite of stages II and III.Stable isotope analyses and fluid inclusion results indicate a magmatic-hydrothermal component in the ore fluids. Fluid inclusion data from stage I yielded the highest salinity (∼6.9 wt% NaCl) and homogenization temperature (average 264 °C). Calculated oxygen isotope composition of fluid (δ18Owater up to 4.9‰) equilibrated with quartz indicates a magmatic-hydrothermal source during stage I. A progressive addition of meteoric water component is suggested from stage I to IV of Zhengguang based on the average δ18Owater values equilibrated with quartz and homogenization temperatures (stage I: δ18Owater = 3.3‰, Th = 264 °C; stage II: δ18Owater = −1.4‰, Th = 182 °C; stage III: δ18Owater = −3.4‰, Th = 154 °C; stage IV: δ18Owater = −6.3‰, Th = 121 °C).Our new pyrite Re-Os dating result shows that Zhengguang formed at the same time with Tongshan and Duobaoshan within errors. Comparable sulfur isotopic compositions of pyrite from Zhengguang and Tongshan, analogous low-Fe content in sphalerite and similar mineral assemblage and alteration pattern between Zhengguang and East Tongshan IS veins collectively indicate a genetic connection between Zhengguang and Tongshan, which may derive from fluids exsolved from the same magma chamber. High-temperature assemblages (e.g., K-feldspr ± pyrite ± chalcopyrite) at Zhengguang indicate that there is potential for the discovery of porphyry copper–gold mineralization below the current level of diamond drilling. The confirmation of the Zhengguang as an Early Paleozoic epithermal deposit implies a good preservation and exploration potential of ancient epithermal deposits in eastern Central Asian Orogenic Belt.