Oxygen Isotope Systematics Research Articles

Hydrogeochemistry of geothermal water in Huangshadong and adjacent areas of Guangdong province: Implications for water-rock interaction

Hydrogeochemical characteristics can reflect important information on the circulation processes of geothermal fluids, reservoir temperatures, etc., which are essential for exploring geothermal field evolution and the rational development of geothermal resources. 23 sets of water samples were collected from Huangshadong and adjacent geothermal fields. Major cations and anions, hydrogen and oxygen isotopes, and 14C activities were analyzed to investigate the hydrogeochemical characteristics of geothermal fluids and their formation mechanisms. Hydrogen and oxygen isotope analysis and major element chemistry indicate that the geothermal waters in the study area are mainly recharged by meteoric water. The chemical facies of the geothermal waters are mainly Na−HCO3 and Ca−HCO3, and most of the geothermal waters have high Na+ contents, which are attributed to the involvement of albite in water-rock interaction and the replacement of Na+ in rocks by Ca2+ or Mg2+ in water. Geothermometry of geothermal waters suggests that the reservoir temperatures are between 140-150 ℃, and the geothermal water circulation depths range from 2.0 to 4.3 km. The residence time of up to 17.3ka for geothermal water likely suggests the earliest precipitation recharge during the Late Pleistocene. Major element chemistry and hydrogen and oxygen isotope systematics indicate essential information on the origins of geothermal waters and water-rock interaction processes and provide a more comprehensive understanding of the geothermal system in Huangshadong and adjacent areas of Guangdong province.

Triple oxygen isotope systematics of CO2 hydroxylation

Kinetic isotope effects occurring during carbonate precipitation impact the accuracy of paleoclimate records. One rate-limiting process is CO2 absorption, which, at high pH, primarily proceeds through hydroxylation, where aqueous CO2 and OH− react to form HCO3−. In this study, we investigated the triple oxygen isotope fractionation (18O/16O and 17O/16O) associated with the hydroxylation reaction. We experimentally determined the extent of the kinetic isotope effects superimposed on the reacting CO2 and OH− during hydroxylation, using high-pH precipitation reactions. These results were compared to the equilibrium triple oxygen isotope fractionation between H2O and OH− modeled using quantum chemical computations.Our quantum chemical modeling confirms the previously suggested equilibrium θeq.H2O/OH- of 0.5296 at 25 °C. Our empirical data show a kinetic isotope effect superimposed on the OH− involved in the hydroxylation reaction of approximately −16.4‰ for the fractionation of 18O/16O and a corresponding slope of 0.514 in triple oxygen isotope space. The θeffectiveH2O/OH- for the fractionation between water and the reacting OH− is 0.523.In order to identify and potentially correct kinetic isotope effects in carbonates, it is important to understand the fractionations occurring during precipitation. Our results enable a more accurate modeling of kinetic isotope effects in triple oxygen isotope space, particularly the slope of hydroxylation. The θhydroxylation is dependent on the isotope composition of the ambient water, CO2, and the temperature. We estimate that θhydroxylation is approximately 0.532 for carbonates growing in 25 °C seawater.

Abiotic aerobic oxidation pathways of stibnite revealed by oxygen and sulfur isotope systematics of sulfate

The environmental threat posed by stibnite is an important geoenvironmental issue of current concern. To better understand stibnite oxidation pathways, aerobic abiotic batch experiments were conducted in aqueous solution with varying δ18OH2O value at initial neutral pH for different lengths of time (15-300 days). The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined. The sulfur isotope fractionation factor (Δ34SSO4-stibnite) values decreased from 0.8‰ to -2.1‰ during the first 90 days, and increased to 2.6‰ at the 180 days, indicating the dominated intermediate sulfur species such as S2O32−, S0, and H2S (g) involved in Sb2S3 oxidation processes. The incorporation of O into sulfate derived from O2 (∼100%) indicated that the dissociated O2 was only directly adsorbed on the stibnite-S sites in the initial stage (0-90 days). The proportion of O incorporation into sulfate from water (27%-52%) increased in the late stage (90-300 days), which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O2 on stibnite-Sb sites. The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42−. The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.

The role of depositional environment and chemical composition on the triple oxygen isotope ratios of ferromanganese precipitates and their endmember components

Ferromanganese precipitates - crusts, nodules, and hydrothermal deposits – typically exhibit negative Δ'17O values. These deviations are thought to reflect partial incorporation of dissolved atmospheric O2, a component with strongly negative Δ'17O values, seawater oxygen, and deep sea O2 into Mn-oxide minerals, in combination with the other major mineralogical endmember components (Fe-oxyhydroxide and silicate minerals), and kinetic processes such as oxidation at mineral surfaces and biological respiration. Our understanding of the triple oxygen isotope systematics of these materials are limited, however; in the current body of literature, triple oxygen isotope data has only been generated for marine hydrogenetic (i.e., metals accrete directly from seawater) Fe-Mn crusts and Mn nodules. This study evaluates the underlying chemical and environmental factors contributing to the bulk triple oxygen isotopic composition of Fe-Mn precipitates of different genetic types (i.e., hydrothermal, hydrogenetic, mixed-type) from a variety of formation environments (e.g., volcanic arc, pull-apart basin, hotspot, freshwater lake). To improve our understanding of the triple oxygen isotope systematics of natural Fe-Mn precipitates and better constrain the endmember components, we isolate and measure close approximations of the Mn-oxide, Fe-oxyhydroxide, and silicate fractions. Hydrothermal Fe-Mn deposits show greater variation in δ'18O and Δ'17O values (6.0 to 29.6 ‰ and −0.286 to 0.007 ‰, respectively) than hydrogenetic Fe-Mn crusts (5.1 to 11.9 ‰ and −0.200 to −0.086 ‰, respectively). Lacustrine Mn nodule δ'18O and Δ'17O values (5.1 to 8.8 ‰ and −0.230 to −0.090 ‰, respectively) are similar to marine hydrogenetic Fe-Mn crusts, primarily reflecting tropospheric O2. The triple oxygen isotope ratios of nearly pure Mn-oxide samples cluster into distinct groups based on oxygen source, and mass-balance mixing models suggest a significant proportion of incorporated oxygen was photosynthetic in origin. The layered Fe-Mn precipitates in this study show irregular to rhythmic patterns of δ'18O and Δ'17O values depending on formation environment that mostly do not correlate with Mn, Fe, and Si contents. Shale-normalized rare earth element and yttrium (REYSN) patterns and anomalies (CeSN/CeSN*, EuSN/EuSN*, and YSN/HoSN), which can provide insight on formation conditions (e.g., redox, oxygen fugacity, and REY speciation of fluids), are compared with the triple oxygen isotope data. The REYSN anomalies increase from the bottom to the top of the profile of the layered marine sample, suggesting conditions became more oxic over time. Although the triple oxygen isotope ratios correlate with the Eu anomaly in most Fe-Mn precipitates, hydrothermal input can limit their utility as indicators of oxygen fugacity. The triple oxygen isotope ratios of Fe-Mn precipitates reflect complex processes and mixing of multiple sources. Constraining these oxygen sources will assist future studies in interpreting paleoenvironmental conditions (e.g., the saturation state and triple oxygen isotope ratios of dissolved O2 in bottom water) at the time of Fe-Mn precipitate formation.

O- and H- Isotope constraints on Neogene high-K calc-alkaline and shoshonitic volcanic rocks and borates in the Kırka (Eskişehir) basin, W Anatolia

ABSTRACT The O and H isotopic ratios of borates, clay minerals, and volcanic rocks from the Kırka basin (south of Eskişehir, W Anatolia) have been analysed in order to better constrain the conditions that led to precipitation of the borates. The δ18Owr values of the volcanic rocks range from + 7.6 to + 15.9‰, but many samples are enriched in 18O by post-eruption hydration, as evidenced by the positive correlation between 18O and H2O (LOI up to 3.1 wt.%) contents. The δ18O values of the borate and clay minerals (smectite) range from 10.0 to 18.8‰, and 19.5 to 31.3‰, respectively. The large variation among the δ18O values of the borate minerals either is likely related to oxygen isotope fractionation during their formation and/or indicates that they formed at different stages of evaporation of the original brines over a range of temperatures. Considering that borax was a primary phase in the basin, decreasing δ18O values from borax to colemanite and ulexite is compatible with decreasing formation temperatures. The δD values of borate and clay minerals do not show significant differences (−64 – −88‰, and −106 – −125‰, respectively). The calculated δ18OH2O and δDH2O values of the fluid in equilibrium with the borate minerals (−11.6–5.93‰ and −85 – −65‰, respectively) and in equilibrium with the smectite (14.4–17.0‰ and −126 – −67‰, respectively) indicates that the basin brines were dominated by geothermal fluids. Overall, the oxygen isotope systematics of the borates and smectite in the Kırka basin are consistent with the smectite and borate minerals forming from brines that resulted from the ponding and evaporation of geothermal fluids that had undergone water-rock interaction with the local felsic volcanic rocks.

Boron and Oxygen Isotope Systematics of Two Hydrothermal Systems in Modern Back-Arc and Arc Crust (PACMANUS and Brothers Volcano, W-Pacific)

AbstractA better characterization of subsurface processes in hydrothermal systems is key to a deeper understanding of fluid-rock interaction and ore-forming mechanisms. Vent systems in oceanic crust close to subduction zones, like at Brothers volcano and in the eastern Manus basin, are known to be especially ore rich. We measured B concentrations and isotope ratios of unaltered and altered lava that were recovered from drilling sites at Brothers volcano and Snowcap (eastern Manus basin) to test their sensitivity for changing alteration conditions with depth. In addition, for Brothers volcano, quartz-water oxygen isotope thermometry was used to constrain variations in alteration temperature with depth. All altered rocks are depleted in B compared to unaltered rocks and point to interaction with a high-temperature (>150°C) hydrothermal fluid. The δ11B values of altered rocks are variable, from slightly lower to significantly higher than those of unaltered rocks. For Brothers volcano, at the Upper Cone, we suggest a gradual evolution from a fluid- to a more rock-dominated system with increasing depth. In contrast, the downhole variations of δ11B at Snowcap as well as δ11B and δ18O variations at the NW Caldera (Site U1530) of Brothers volcano are suggested to indicate changes in water-rock ratios and, in the latter case, also temperature, with depth due to permeability contrasts between different lithology and alteration type boundaries. Furthermore, δ11B values from the NW Caldera (Site U1527) might point to a structural impact on the fluid pathway. These differences in the subseafloor fluid flow regime, which ranges from more pervasive and fluid-controlled to stronger and controlled by lithological and structural features, have significant influence on alteration conditions and may also impact metal precipitation within the sea floor.

Transformation mechanism of methylphosphonate to methane by Burkholderia sp: Insight from multi-labeled water isotope probing and transcriptomic

Methylphosphonate (MPn), has been identified as a likely source of methane in aerobic ocean and may be responsible for the “ocean methane paradox”, that is oversaturation of dissolved methane in oxic sea waters. However, the mechanism underlying the cleavage of C–P bonds during microbial degradation is not well understood. Using multi-labeled water isotope probing (MLWIP) and transcriptome analysis, we investigated the phosphate oxygen isotope systematics and mechanisms of microbial-mediated degradation of MPn in this study. In the aerobic culture containing MPn as the only phosphorus source, there was a significant release of inorganic phosphate (149.4 μmol/L) and free methane (268.3 mg/L). The oxygen isotopic composition of inorganic phosphorus (δ18OP) of accumulated released phosphate was 4.50‰, 23.96‰, and 40.88‰, respectively, in the corresponding 18O-labeled waters of −10.3‰, 9.9‰, and 30.6‰, and the slope obtained in plots of δ18OP versus the oxygen isotopic composition of water (δ18OW) was 0.89. Consequently, 89% of the oxygen atoms (Os) in phosphate (PO4) were exchanged with 18O-labeled waters in the medium, while the rest were exchanged with intracellular metabolic water. It has been confirmed that the C–P bond cleavage of MPn occurs in the cell with both ambient and metabolic water participation. Moreover, phn gene clusters play significant roles to cleave the C–P bond of MPn for Burkholderia sp. HQL1813, in which phnJ, phnM and phnI genes are significantly up-regulated during MPn decomposition to methane. In conclusion, the aerobic biotransformation of MPn to free methane by Burkholderia sp. HQL1813 has been elucidated, providing new insights into the mechanism that bio-cleaves C–P bonds to produce methane aerobically in aqueous environments for representative phosphonates.

Kinetic isotope effects in H2O2 self-decomposition: Implications for triple oxygen isotope systematics of secondary minerals in the solar system

Hydrogen peroxide (H2O2) is a ubiquitous molecule in nature that shapes the redox state of planetary surfaces. Given that H2O2 is a major oxidant, isotope effects associated with H2O2 chemistry play a key role in determining triple oxygen isotopic compositions (δ17O and δ18O) of secondary aerosols and minerals, which are powerful proxies for understanding terrestrial/Martian atmospheric chemistry, and chemical evolution in the solar nebular. However, isotope effects in H2O2 self-decomposition processes, which actively occur in nature due to the thermal instability of H2O2, remains poorly understood. Here, we report a hitherto overlooked large and mass-dependent isotope fractionation in aqueous H2O2 self-decomposition processes quantified in a series of kinetic experiments. δ18O in remaining H2O2 is several tens of per mil (‰) with respective to initial H2O2. By synthesizing triple oxygen isotope measurements of natural H2O2, ozone, various oxyanions formed in the atmosphere (sulfate, nitrate, perchlorate, and carbonate), and oxygen-bearing secondary minerals in meteorites, we find that a decoupled Δ17O–δ18O pattern in natural H2O2 is attributed in part to the high degree of mass-dependent δ18O variation in H2O2 decomposition, and further argue that this unique signature may play a crucial role in triple oxygen isotope systematics in a board spectrum of secondary minerals in our solar system including aerosols, sediments, and meteorites. Our results shed fresh insights into recent debates on the role of H2O2 in the formation of these secondary minerals in the modern Earth, geological past, and other planets. The isotope effect experimentally quantified in this study are needed for future improvements of planetary atmosphere and solar nebular evolution models. We highlight the importance of further experimental and theoretical efforts to quantify isotope effects in H2O2 chemistry that are representative of natural systems.

Sulfur and Oxygen Isotope Records of Sulfate-Driven Anaerobic Oxidation of Methane in Diffusion-Dominated Marine Sediments

Organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM) are the two major microbial pathways for sulfate consumption in marine sulfur cycle. The relative changes of sulfur and oxygen isotope ratios in pore water sulfate are affected by the mode of microbial sulfate reduction and have been applied as an indicator for assessing methane excess environments. However, so far, this isotope proxy fails to distinguish sulfate reduction processes fueled by the oxidation of organic matter or by diffusing methane. To better understand the mechanism of sulfur and oxygen isotope partitioning during OSR and SD-AOM, coupled sulfur and oxygen isotopic compositions of pore water sulfate (δ34SSO4 and δ18OSO4) were investigated from four methane diffusing sites (CL56, CL57, CL59, and CL60) of the South China Sea, supplemented by carbon isotopic composition of dissolved inorganic carbon (DIC) and sulfur isotopic composition of pyrite in bulk sediments. Pore water sulfate and DIC concentrations, as well as calculated net sulfate reduction rates suggest that the sulfate reduction at site CL57 was mainly dominated by OSR, whereas sites CL56, CL59, and CL60 were likely impacted by both OSR and SD-AOM. Furthermore, the trend of cross-plotting δ18OSO4 versus δ34SSO4 values from site CL57 was distinguishable from sites CL56, CL59, and CL60, although all study sites show similar patterns to those derived from methane limited environments. This further indicates the trajectory of sulfur and oxygen isotope partitioning was affected by the mode of sulfate reduction (i.e., OSR vs. SD-AOM). At site CL57, the low net sulfate reduction rate would lead to enhanced oxidation of intermediate sulfur species during OSR, thus leading to a higher slope in the δ18OSO4 vs. δ34SSO4 cross-plot (1.26). In contrast, the higher net sulfate reduction rates at sites CL56, CL59, and CL60 due to the impact from SD-AOM would lead to lower slopes in the δ18OSO4 vs. δ34SSO4 cross-plots (0.78 ± 0.11). This study provides new insights into the sulfur and oxygen isotope systematics during microbial sulfate reduction processes in methane diffusing environments.

In-situ O-isotope analysis of relict spinel and forsterite in small (

We report high-precision secondary ion mass spectrometer triple oxygen isotope systematics (95 individual analyses) from 37 micrometeorites (MMs) collected from South Pole Water Well (SPWW), Antarctica. The study population focuses on unmelted coarse-grained (Cg) MMs (n = 23) with both multiple (n = 14) and single-mineral (n = 9) varieties investigated. We also analysed relict minerals in porphyritic cosmic spherules (n = 13) and the relict matrix in a single scoriaceous fine-grained (Fg) MM. The target minerals investigated are primarily olivine (Fo ∼ 43–99%) and spinel. Textural, chemical and isotopic data confirm that both olivine and spinel grains have retained their pre-atmospheric O-isotope compositions, allowing inferences to be drawn about their formation and parent body affinities. We separate the study population into three groups: spinel-free particles (consisting of the CgMMs and PO cosmic spherules), spinel-bearing MMs and the single FgMM.Olivine grains in spinel-free MMs vary between δ17O: −12.6‰ and +3.5‰, δ18O: −9.6‰ and +7.5‰, and Δ17O: −9.5‰ and +1.3‰ and define a slope-1 profile in δ18O–δ17O isotope space. They are most likely fragmented chondrules, with both type I and type II varieties represented. Their observed Mg#-Δ17O distribution is best explained by a mixture of CM chondrules and either CR chondrules, Tagish Lake chondrules or WILD2 cometary silicates. One of these chondrule-like MMs has an isotopically heterogeneous composition, characterised by a single olivine grain with a markedly 16O-rich composition (Δ17O: −16.3‰), suggesting it is a relict silicate fragment of AOA material that was incorporated into the chondrule precursor.We analysed 11 spinel grains in five spinel-bearing MMs. In all instances spinels are nearly pure MgAl2O4 with isotopically light (16O-rich) compositions (ranging from δ17O: −34.4‰ to −0.9‰, δ18O: −30.8‰ to +11.0‰, and Δ17O: −18.3‰ to −4.4‰). They are therefore 16O-poor relative to spinel found in unaltered CAIs, indicating a different origin. Grains with high Cr2O3 contents (>0.5 wt.%) are interpreted originating from Al-rich chondrule precursors, while low Cr2O3 spinels (<0.5 wt.%) are interpreted as CAI-derived material affected by parent body aqueous alteration.Finally, we report a single FgMM with a 16O-poor composition (Δ17O > 0‰ and δ18O > +15.0‰). This particle adds to our growing inventory of water-rich C-type asteroid samples united by their formation history which is characterised by accretion of abundant heavy water.Our work strongly supports findings from earlier in-situ O-isotope studies, concluding that small MMs overwhelmingly sample material from CC parent bodies and that CgMMs largely sample chondrules and, to a lesser extent, CAI material. The analysis of CgMMs therefore provides insights into the primitive O-isotope reservoirs that were present in the early solar system and how they interacted.

Towards a holistic sulfate-water-O2 triple oxygen isotope systematics

Triple oxygen isotope (∆17O with δ18O) signals of H2O and O2 found in sulfate of oxidative weathering origin offer promising constraints on modern and ancient weathering, hydrology, atmospheric gas concentrations, and bioproductivity. However, interpretations of the sulfate-water-O2 system rely on assuming fixed oxygen-isotope fractionations between sulfate and water, which, contrastingly, are shown to vary widely in sign and amplitude. Instead, here we anchor sulfate-water-O2 triple oxygen isotope systematics on the homogeneous composition of atmospheric O2 with empirical constraints and modeling. Our resulting framework does not require a priori assumptions of the O2- versus H2O‑oxygen ratio in sulfate and accounts for the signals of mass-dependent and mass-independent fractionation in the ∆17O and δ18O of sulfate's O2‑oxygen source. Within this framework, new ∆17O measurements of sulfate constrain ~2.3 Ga Paleoproterozoic gross primary productivity to between 6 and 160 times present-day levels, with important implications for the biological carbon cycle response to high CO2 concentrations prevalent on the early Earth.

Triple oxygen isotope systematics of diagenetic recrystallization of diatom opal-A to opal-CT to microquartz in deep sea sediments

The oxygen-18 isotopic composition (δ18O) of silica preserved in oceanic sediments is an important archive of Earth’s temperature and/or seawater δ18O from the Archean to present. Recent advances in high-precision measurements of both δ18O and δ17O values have been used to provide additional constraints on what the oxygen isotopic composition of chert reflects about past conditions. Here, we examine the effects on the triple oxygen isotopic composition of chert that occurs during transformation and recrystallization of biogenic opal-A to opal-CT to microquartz in deep sea sediments. We studied late Miocene to present samples from the Sea of Japan at ODP Site 795 and measured biogenic diatom opal-A, opal-CT, microquartz chert, and ‘altered’ opal-A samples—previously measured for δ18O values only—for both δ18O and δ17O values. We find that δ18O decreases and Δ′17O increases (where Δ′17O = δ17O – 0.528 × δ18O) with depth, coincident with the conversions from diatom opal-A to opal-CT to microquartz. Silica samples deviate from the trend expected for triple oxygen isotopic equilibrium with modern seawater. To explain these data, we developed a model that shows that local temperature gradients and pore fluid δ18O profiles in combination lower the measured opal-CT and microquartz δ18O values and raise the Δ′17O values relative to the initial opal-A, but deviate from triple oxygen isotopic equilibrium with seawater. We find that a steeper local temperature gradient and a larger influence of hydrothermal alteration of basalt at the base of the sediment column (which lowers pore fluid δ18O values) in the past explain both the measured δ18O and Δ′17O values of the opal-CT and microquartz.These data and our modeling show that the transformation of opal-A to microquartz in marine sediments at elevated temperatures and in the presence of lowered pore water δ18O values leads to an array that falls below the theoretical triple oxygen isotope line of equilibrium for SiO2 with modern seawater. Further, our model indicates that opal-CT and microquartz do form in triple oxygen isotopic equilibrium with pore fluids that are offset in their triple oxygen isotopic composition compared to seawater due to fluid-rock alteration of igneous rocks at the base of the sediment column. The diagenetic processes taking place in the Japan Sea do not explain a large portion of the existing Archean to present triple oxygen isotope chert data, which likely require either changes in the oxygen isotopic composition of the source water (i.e., ocean water) and/or alteration by meteoric fluids. Further, our data demonstrate that the triple oxygen isotopic composition of preserved chert need not represent surface conditions, but instead may reflect processes that occur in subsurface sediments at elevated temperatures and with modified pore fluid oxygen isotopic compositions.

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.

Cosmic symplectite recorded irradiation by nearby massive stars in the solar system's parent molecular cloud

The Sun’s astrophysical birth environment affected the formation and composition of the Solar System. Primitive meteorites display mass-independent oxygen isotope anomalies that were likely caused by ultraviolet (UV) photochemistry of CO gas-phase molecules, either (i) in the outer solar nebula by light from the young Sun or (ii) in the parent molecular cloud by light from nearby stars. However, measurements of oxygen isotopes alone cannot unambiguously constrain the UV spectrum of the source responsible for the photochemistry. Sulfur, with four stable isotopes, can be used as a more direct probe of the astrophysical environment of mass-independent photochemistry. Here, we report the in situ isotopic analysis of paired oxygen and sulfur isotope systematics in cosmic symplectite (COS), magnetite-pentlandite intergrowths, in the primitive ungrouped carbonaceous chondrite Acfer 094. We show that COS grains contain mass-independent sulfur isotope anomalies (weighted means of Δ33S = +3.84 ± 0.72‰ and Δ36S = −6.05 ± 2.25‰, 2SE) consistent with H2S photochemistry by UV from massive O and B stars close to the Solar System’s parent molecular cloud, and inconsistent with UV from the protosun. The presence of coupled mass-independent sulfur and oxygen (Δ17O = 86 ± 6‰, 2SE) isotope anomalies in COS imply that these anomalies originated in the same astrophysical environment. We propose that this environment is the photodissociation region (PDR) of the Solar System’s parent molecular cloud, where nearby massive stars irradiated the edge of the cloud. We conclude that the Sun’s stellar neighbors, likely O and B stars in a massive-star-forming region, affected the composition of the Solar System’s primordial building blocks.

Oxygen isotope systematics of crystalline silicates in a giant cluster IDP: A genetic link to Wild 2 particles and primitive chondrite chondrules

Anhydrous interplanetary dust particles (IDPs) collected from Earth's stratosphere are the most primitive extraterrestrial materials that likely are the remnants of major building blocks of our solar system. While they probably originated from icy outer solar system comets, this hypothesis needs to be further verified via comparison with Wild 2 (a Jupiter-family comet) particles returned by the Stardust mission. Besides, the origins of their components can be further constrained by comparing with materials in primitive chondrite. Here we investigate the petrology and oxygen isotope systematics of 20 fragments extracted from a giant cluster IDP U2-20GCA. Fifteen are monomineralic or polymineralic fragments composed of olivine and/or pyroxene. Others are plagioclase/glass bearing fragments similar to barred-olivine chondrules, enstatite-rich chondrules, and Al-rich chondrules (ARC). They show a range of Mg# [mol% Mg/(Mg+Fe)] in olivine and pyroxene (99-75) and MnO and Cr2O3 abundances in olivine that resemble Wild 2 particles. Individual fragments have relatively 16O-poor oxygen isotope ratios with δ18O and δ17O varying from −6.2±1.0‰ to 6.8±1.9‰ and −6.7±2.6‰ to 5.3±1.2‰, respectively. Most fragments show Δ17O (=δ17O-0.52×δ18O) increasing from ∼−3‰ to ∼0‰ with decreasing Mg#, similar to those observed in Wild 2 particles and CR chondrite chondrules. Four fragments (including the ARC-like fragment) show oxygen isotope signatures of ordinary (O), R, or CH-CB chondrite chondrules. The similarities among the giant cluster IDP, Wild 2 particles, and primitive chondrite chondrules demonstrate (i) a cometary origin of anhydrous IDPs; (ii) the major source of crystalline silicates in comets is likely to be CR chondrite chondrule-like materials, while minor sources include O, R, or CH-CB chondrite chondrule-like materials. The conclusions support the hypothesis that anhydrous IDPs sampled extremely heterogeneous materials formed in wide solar system regions like Wild 2 particles.

Element mobility and oxygen isotope systematics during submarine alteration of basaltic glass

Abstract Studies of the submarine alteration of basaltic glass may improve the understanding of crust-seawater interactions and the oceanic elemental cycle. Natural alteration processes such as the palagonitization of basaltic glass are complex, and their elucidation is crucial to the understanding of fluid-rock interactions. This study involves major and trace element and isotope mapping of a submarine-altered basaltic glass grain and reveals sequential development of alteration textures toward the grain core through the transition between unaltered glass and palagonite. The conversion from basaltic glass to palagonite in a low-temperature submarine environment results in enrichment in B, Rb, K, Li, H2O, U, Nb, Th, Ti, Cu, Ta, Zr, Hf, Ni, Sc, Fe, Cr, Pb, and Zn; and depletion in Si, Mg, Al, Sr, Na, Co, rare-earth elements, Ca, P, and V (in order of decreasing distribution coefficient). The glass-palagonite interface region has the highest high field strength element (HFSE) and Fe-Ti contents but the lowest Mg content, indicating that the Fe-Ti phases that host HFSE were precipitated first during initial palagonitization. At the same time, an inferred exchange of oxygen occurred, based on variation in δ18O, with values increasing from basaltic glass to palagonite. However, initial palagonite compositions were affected by subsequent precipitation and/or incorporation/adsorption of additional compounds such as Mg(OH)2 scavenged from pore water.

Comment on "Correlation of the stratigraphic cover of the Pilbara and Kaapvaal cratons recording the lead up to Paleoproterozoic Icehouse and the GOE" by Andrey Bekker, Bryan Krapež, and Juha A. Karhu, 2020, Earth Science Reviews, https://doi.org/10.1016/j.earscirev.2020.103389

Triple oxygen isotope (∆17O with δ18O) signals of H2O and O2 found in sulfate of oxidative weathering origin offer promising constraints on modern and ancient weathering, hydrology, atmospheric gas concentrations, and bioproductivity. However, interpretations of the sulfate-water-O2 system rely on assuming fixed oxygen-isotope fractionations between sulfate and water, which, contrastingly, are shown to vary widely in sign and amplitude. Instead, here we anchor sulfate-water-O2 triple oxygen isotope systematics on the homogeneous composition of atmospheric O2 with empirical constraints and modeling. Our resulting framework does not require a priori assumptions of the O2- versus H2O‑oxygen ratio in sulfate and accounts for the signals of mass-dependent and mass-independent fractionation in the ∆17O and δ18O of sulfate's O2‑oxygen source. Within this framework, new ∆17O measurements of sulfate constrain ~2.3 Ga Paleoproterozoic gross primary productivity to between 6 and 160 times present-day levels, with important implications for the biological carbon cycle response to high CO2 concentrations prevalent on the early Earth.

Triple oxygen isotope systematics of evaporation and mixing processes in a dynamic desert lake system

Abstract. This study investigates the combined hydrogen deuterium and triple oxygen isotope hydrology of the Salar del Huasco, an endorheic salt flat with shallow lakes at its centre that is located on the Altiplano Plateau, N Chile. This lacustrine system is hydrologically dynamic and complex because it receives inflow from multiple surface and groundwater sources. It undergoes seasonal flooding, followed by rapid shrinking of the water body at the prevailing arid climate with very high evaporation rates. At any given point in time, ponds, lakes, and recharge sources capture a large range of evaporation degrees. Samples taken between 2017 and 2019 show a range of δ18O between −13.3 ‰ and 14.5 ‰, d-excess between 7 ‰ and −100 ‰, and 17O-excess between 19 and −108 per meg. A pan evaporation experiment conducted on-site was used to derive the turbulence coefficient of the Craig–Gordon isotope evaporation model for the local wind regime. This, along with sampling of atmospheric vapour at the salar (-21.0±3.3 ‰ for δ18O, 34±6 ‰ for d-excess and 23±9 per meg for 17O-excess), enabled the accurate reproduction of measured ponds and lake isotope data by the Craig–Gordon model. In contrast to classic δ2H–δ18O studies, the 17O-excess data not only allow one to distinguish two different types of evaporation – evaporation with and without recharge – but also to identify mixing processes between evaporated lake water and fresh flood water. Multiple generations of infiltration events can also be inferred from the triple oxygen isotope composition of inflow water, indicating mixing of sources with different evaporation histories. These processes cannot be resolved using classic δ2H–δ18O data alone. Adding triple oxygen isotope measurements to isotope hydrology studies may therefore significantly improve the accuracy of a lake's hydrological balance – i.e. the evaporation-to-inflow ratio (E / I) – estimated by water isotope data and application of the Craig–Gordon isotope evaporation model.

Oxygen isotope systematics of chondrules in the Paris CM2 chondrite: Indication for a single large formation region across snow line

In-situ oxygen three-isotope analyses of chondrules and isolated olivine grains in the Paris (CM) chondrite were conducted by secondary ion mass spectrometry (SIMS). Multiple analyses of olivine and/or pyroxene in each chondrule show indistinguishable Δ17O values, except for minor occurrences of relict olivine grains (and one low-Ca pyroxene). A mean Δ17O value of these homogeneous multiple analyses was obtained for each chondrule, which represent oxygen isotope ratios of the chondrule melt. The Δ17O values of individual chondrules range from −7‰ to −2‰ and generally increase with decreasing Mg# of olivine and pyroxene in individual chondrules. Most type I (FeO-poor) chondrules have high Mg# (∼99) and variable Δ17O values from −7.0‰ to −3.3‰. Other type I chondrules (Mg# ≤97), type II (FeO-rich) chondrules, and two isolated FeO-rich olivine grains have host Δ17O values from −3‰ to −2‰. Eight chondrules contain relict grains that are either 16O-rich or 16O-poor relative to their host chondrule and show a wide range of Δ17O values from −13‰ to 0‰.The results from chondrules in the Paris meteorite are similar to those in Murchison (CM). Collectively, the Δ17O values of chondrules in CM chondrites continuously increase from −7‰ to −2‰ with decreasing Mg# from 99 to 37. The majority of type I chondrules (Mg# >98) show Δ17O values from −6‰ to −4‰, while the majority of type II chondrules (Mg# 60–70) show Δ17O values of −2.5‰. The covariation of Δ17O versus Mg# observed among chondrules in CM chondrites may suggest that most chondrules in carbonaceous chondrites formed in a single large region across the snow line where the contribution of 16O-poor ice to chondrule precursors and dust enrichment factors varied significantly.

Triple Oxygen Isotope Systematics in the Hydrologic Cycle

Research Article| January 01, 2021 Triple Oxygen Isotope Systematics in the Hydrologic Cycle Jakub Surma; Jakub Surma Institute of Geology and Mineralogy, University of Cologne, Zülpicher Straße 49b, Cologne, 50674, GermanyPresently at: Geoscience Center, Georg August University, Goldschmidtstraße 1 Göttingen, 37077, Germany * E-mail: jakub.surma@uni-goettingen.de Search for other works by this author on: GSW Google Scholar Sergey Assonov; Sergey Assonov Formerly at: Institute of Geology and Mineralogy, University of Cologne, Zülpicher Straße 49b Cologne, 50674, Germany Search for other works by this author on: GSW Google Scholar Michael Staubwasser Michael Staubwasser Institute of Geology and Mineralogy, University of Cologne, Zülpicher Straße 49b Cologne, 50674, Germany Search for other works by this author on: GSW Google Scholar Reviews in Mineralogy and Geochemistry (2021) 86 (1): 401–428. https://doi.org/10.2138/rmg.2021.86.12 Article history first online: 04 Jan 2021 Cite View This Citation Add to Citation Manager Share Icon Share Twitter LinkedIn Tools Icon Tools Get Permissions Search Site Citation Jakub Surma, Sergey Assonov, Michael Staubwasser; Triple Oxygen Isotope Systematics in the Hydrologic Cycle. Reviews in Mineralogy and Geochemistry 2021;; 86 (1): 401–428. doi: https://doi.org/10.2138/rmg.2021.86.12 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyReviews in Mineralogy and Geochemistry Search Advanced Search The analysis of hydrogen (δD) and oxygen (δ18O) isotope ratios of H2O are widely used tools for studies of the hydrological cycle (Friedman 1953; Dansgaard 1954; Gonfiantini 1986; Gat 1996; Araguás-Araguás et al. 2000; Gat et al. 2000) and climate reconstruction (Dansgaard 1964; Johnsen et al. 1989; Petit et al. 1999). Natural variations of δD and δ18O in precipitation are well correlated and fall on a common global trend, the Global Meteoric Water Line (GMWL, Craig 1961): δD=8·... You do not have access to this content, please speak to your institutional administrator if you feel you should have access.