Triple Oxygen Research Articles

Seawater-oceanic crust interaction constrained by triple oxygen and hydrogen isotopes in rocks from the Saglek-Hebron complex, NE Canada: Implications for moderately low-δ18O Eoarchean Ocean

Estimations of Earth's earliest surface conditions assume a strong connection between the temperature and oxygen isotopic composition of oceans, balanced by surface weathering and submarine hydrothermal alteration. The oldest preserved supracrustal rocks provide rare opportunities to study and constrain the earliest surface conditions prevailing on the Earth. Here, we present a study of triple oxygen and hydrogen isotopes of hydrothermally altered Eoarchean metamorphosed basalts, ultramafic rocks, and detrital and chemical sediments, from the Saglek-Hebron Complex in northern Labrador, Canada. For the metavolcanic rocks, δ’18O values range from 4.83 ‰ to 8.56 ‰, while Δ’17O values vary from −0.076 ‰ to −0.023 ‰, both higher and lower than the mantle. Accounting for the effects of metamorphism on oxygen and hydrogen isotopic compositions, we demonstrate that triple oxygen isotopic values are preserved from the hydrothermal suboceanic stage, while none of the hydrogen isotope compositions (δD from −77.9 ‰ to −10.7 ‰) are interpreted as primary. Several metabasalt samples from the Saglek-Hebron Complex yielded Δ’17Ο values lower than modern mantle values, which cannot be explained by direct interaction with modern seawater and indicate complex upstream interactions. Our numerical models and Monte Carlo simulation considers one- and two-stage mechanisms of water-rock interaction, including the δ’18Ο and Δ’17Ο isotopic shift effects due to interaction between basalts and chemical sediment-derived fluids. The modelling favors Eoarchean seawater characterized by low δ’18Ο < −8 ‰ at Δ’17Ο up to 0.01 ‰. This model also works for higher Δ’17Ο at lower δ’18Ο. Our results also suggest that without proper modelling of multi-stage water-rock interaction, involving isotopic shifts and input of sediment-derived fluids, exposed sections of altered oceanic crust present only remote evidence of the original seawater. Due to the modeled isotopic shifts and fluid mixing, we favor “weak” coupling of seawater-oceanic crust interaction globally. This potentially reduces the relative importance of submarine hydrothermal alteration in explaining the oxygen isotopic record in submarine basalts across the geologic history.

Quantitative Conversion of Sulfate Oxygen for High-Precision Triple Oxygen Isotope Analysis.

Triple oxygen isotope composition (Δ'17O) of sulfate carries information on the sulfur cycle as well as signatures of atmospheric O2, O3, and surface water of the geological past. However, existing analytical techniques can only achieve a partial oxygen yield during the conversion from sulfate to the analyte O2, which results in isotope fractionation and impedes the Δ'17O comparison with other oxygen-bearing compounds (e.g., H2O) on the VSMOW-SLAP scale. Here, we present an analytical method involving high-temperature graphite reduction, CO discharge, and Pt-catalyzed CO2-O2 isotope exchange, the R-D-E method, that achieves ∼100% conversion of sulfate oxygen to CO2. Compared with the widely used CO2-laser-fluorination technique, our R-D-E method has a better Δ'17O precision (9 per meg) and requires a smaller sample amount, as low as 4 μmol of sulfate (equivalent to 1 mg BaSO4), with both Δ'17O and δ18O being determined simultaneously. Using this method, we report the triple oxygen isotope compositions of three international reference materials (NBS-127, IAEA-SO-5, and IAEA-SO-6) and three in-house references on the VSMOW-SLAP scale. We found that the sulfate Δ'17O values measured on the partially yielded O2 from the fluorination technique are 10-200 per meg higher than those obtained by our R-D-E method, depending on the oxidant used (e.g., F2 or BrF5). Incomplete conversion of sulfate oxygen during the high-temperature graphite reduction would result in lower δ18O and higher Δ'17O values. This work highlights the needs for recalibration and reinterpretation of the published sulfate Δ'17O data when sulfate Δ'17O values of interest are small.

17O-excess of grass leaf phytoliths across the North American prairies records late-growing season daytime relative humidity

Because it is an important climate parameter, an accurate proxy is required for the reconstruction of past Relative Humidity (RH). Triple oxygen isotopes of grass-leaf phytoliths have a high potential for this purpose. A strong correlation between RH and 17O-excess of grass leaf phytoliths has been previously demonstrated from calibration experiments in growth chambers and at natural Sub-Saharan African and Mediterranean sites. Here we focus on the potential of 17O-excess of grass leaf phytoliths as a proxy of RH across the North American Great Plains. We tested the relationship between the 17O-excess of naturally grown Calamovilfa longifolia phytoliths and RH for different periods of the grass growing season. The results show that 17O-excess of leaf phytoliths has a strong correlation with late-growing season (July–August) daytime RH, which varies from 29 to 72 % across North America. The correlation can be expressed as: 17O-excessleaf phytoliths = 4.14(±0.47) × RH (%) – 497(±26) (R2 = 0.85, p-value<0.0001), which is statistically equal to the previous calibration equation (Alexandre et al., 2018; Outrequin et al., 2021). To use the 17O-excess of bulk phytoliths from buried soils and sediments as a quantitative proxy of past RH, future calibration studies on soil phytoliths are needed to evaluate the contribution of non-transpiring phytoliths. The 17O-excess of stem water, which was determined by 17O-excess of stem phytoliths, shows similar values to the 17O-excess of precipitation in North America without evaporation, which therefore does not affect the 17O-excess of leaf phytoliths in North America. These results demonstrate that the 17O-excess of phytoliths is a promising proxy for regional growing season RH.

Triple oxygen and hydrogen isotopes of glacial diamictites record crustal maturation and changing surface conditions through geologic time

The triple oxygen and hydrogen stable isotopic compositions of 24 glacial diamictite composites with depositional ages from 2.9 to 0.3 Ga are used to reconstruct the evolution of the continental crust and surface environments. The δ18O of the diamictite composites increases from the Archean to the Phanerozoic by ∼4 ‰ (3–5 ‰ in Mesoarchean to 13.5 ‰ in Neoproterozoic), a trend that is comparable to those seen in shales and granites, although the diamictites plot on the lower δ18O end of the range seen in shales. The Δ’17O0.528 decreases from −0.04 to −0.15 ‰, overlapping with shales and granites. Nine zircon separates extracted from individual diamictites also show a ∼3 ‰ increase in δ18O from 3.75 to 4.5 ‰ to 7 ‰ between 2.9 and 0.6 Ga. The δ18O of diamictites and zircon separates negatively correlates with ɛNd(i) of the diamictites, suggesting that the longer the rocks reside in the upper continental crust (the lower the ɛNd), the more they are subjected to repeated weathering cycles, thus acquiring a higher δ18O and lower Δ’17O0.528 during each cycle. On a triple O isotope plot (δ17O vs δ18O), diamictites define an array with a slope of 0.523, analogous to granites and shales.The δD values of nearly all diamictites overlap with the typical mantle and crustal ranges of −58 ± 12 ‰ and − 69 ± 24 ‰, respectively, but are on the lower end of coeval shale values. Water, contained primarily in sheet silicates, ranges from 2.85 wt% (pre-2.4 Ga) and 2.35 wt% (post-2.4 Ga), showing no temporal change, likely reflecting post-depositional reset. The youngest diamictites (0.3 Ga Dwyka Group) exhibit low δD values of −105 to −111 ‰, lower than the typical crustal values, potentially reflecting the near-polar position of South Africa at the time of their deposition, which is corroborated by the reconstructed δ18O value of −26 ‰ based on triple oxygen isotopic systematics.The chemical index of alteration (CIA) allows inverting measured δ18O and Δ’17O values of diamictite composites into a pure weathering product (wp) end member by subtracting values of coeval unweathered crust based on tzircon δ18O. This reveals that the δ18Owp also increases with time, suggesting that the increase in δ18O (decrease in Δ’17O) of the maturing crust is insufficient to fully explain the trends. Therefore, at least part of the increasing δ18Owp likely reflects increasing δ18O of the hydrosphere. Reconstructed surface temperatures around the time of diamictite deposition using δ18Owp and Δ’17Owp display a general decrease since the Archean. Given the diagenetic and post-diagenetic history experienced by the diamictites, the temporal and global trends should be interpreted with caution. Nonetheless, reconstructed δ18Owater shows an increase from −21 ‰ at 2.9 Ga to −11 ‰ at 0.6 Ga. Thus, diamictites, like shales, broadly monitor the evolution of surface conditions on Earth from warmer to colder and from lower to higher δ18Owater values of the hydrosphere.

Triple oxygen isotope variability of precipitation in a tropical mountainous region

We present one year of δD, δ18O, d-excess, and Δʹ17O data from monthly precipitation at a Caribbean coastal site in Panama and from tap waters across the country to constrain geographic, climate, and moisture source controls on isotopic variability and better understand the sources and mechanisms of precipitation in Central America, a region facing significant modifications to the annual rainfall cycle due to climate change. Monthly precipitation δD ranged from –52.2 to +14.3 ‰, δ18O from –7.6 to +0.4 ‰, d-excess from +7.1 to +11.6 ‰, and Δ′17O from +11 to +29 per meg. Rainy season precipitation samples were found to have lower δD, δ18O, and d-excess due to Rayleigh distillation during the condensation and rainout of Pacific moisture over the central cordilleras, which results in decoupling between d-excess and Δ′17O. Outlier Δ′17O values during peak dry and rainy months may reflect seasonal changes in water vapor sourcing, from Caribbean to Pacific and/or locally recycled moisture, or may be a result of organic contamination. Tap water δD ranged from –82.3 to –14.3 ‰, δ18O from –11.6 to –2.4 ‰, d-excess from +4.3 to +12.2 ‰ and Δ′17O from –2 to +84 per meg. Tap water δD and δ18O values increase eastward due to lower orographic effects and Pacific and locally recycled moisture contributions to rainfall and greater secondary evaporation. Tap water d-excess and Δ′17O values are also de-coupled but lack clear spatial trends and controls. The results of this study indicate the promise of adding Δ′17O to the isotopic toolkit in tropical mountainous regions with complicated water cycling dynamics and provide a baseline for future triple oxygen isotope investigations.

World-class amethyst-agate geodes from Los Catalanes, Northern Uruguay: genetic implications from fluid inclusions and stable isotopes

AbstractThe amethyst and agate geodes from the Los Catalanes Gemmological District in Uruguay represent one of the main deposits of its kind worldwide. The geometry of the deposit is horizontal, with an irregular distribution of amethyst geodes within the upper level of the basalt lava flows and shows strong variations in their abundance, as well as quality, geometry, and shape. Reliable exploration guides are scarce, and the limited knowledge of the geological parameters controlling its occurrence makes exploration unpredictable, leading to inaccurate reserve estimation. Based on cutting-edge methods including nucleation-assisted microthermometry of one-phase fluid inclusions and determination of triple oxygen isotope in silicates and carbonates, as well as analysis of geode-hosted water and groundwater, we estimate the crystallisation temperatures in the range between 15 and 60 °C. These low temperatures point to amethyst crystallisation after the emplacement of the complete basalt pile. The mineralising fluid shows isotopic signatures consistent with meteoric water and very low salinities from pure water up to rarely over 3 wt% NaCl-eq., likely sourced from the groundwater hosted in the aquifers in the basaltic sequence and underlying units. Based on the insights provided by the new data, we propose the combination of open- and closed-system crystallisation inside pre-existing cavities due to the episodic infiltration of meteoric water in a rather stable geological context.

Triple oxygen isotope reveals insolation-forced tropical moisture cycles.

Tropical oceans are the main global water vapor and latent heat sources, but their responses to radiative forcing remain unclear. Here, we investigate oceanic moisture dynamics of the western tropical Pacific (WTP) over the past 210,000 years through an approach of planktonic foraminiferal triple oxygen isotope (Δ'17O). The Δ'17O record is dominated by the precession cycles (~23,000 years), with lower values reflecting higher humidity in concert with higher Northern Hemisphere summer insolation. Our empirical and modeling results, combined with other geological archives, suggest that the enhanced moisture convergence over the WTP largely intensifies changes in the meridional and zonal hydrological cycles, affecting rainfall patterns in East Asia and northern South America. We propose that the insolation-driven WTP moisture dynamics play a pivotal role in regulating tropical hydroclimate.

Seasonal Variations and Controls on Triple Oxygen and Hydrogen Isotopes in Precipitation—A Case Study From Monitoring in Southwest China

AbstractPrecipitation δ18O has offered valuable insights into the evolution of the Asian monsoon. Recent researches focusing on precipitation Δ′17O has enhanced our understanding by offering new perspectives beyond those of δ18O, revealing insights into vapor sources and continental recycling. Nevertheless, there remains a lack of interannual triple oxygen isotope data, particularly in the Asian monsoon region. In this study, we analyzed the triple oxygen isotopes and hydrogen isotopes in monthly precipitation samples collected from Chongqing in Southwest China between 2019 and 2022 A.D. Seasonal variations in δD, δ18O, δ17O, and d‐excess values were observed, with lower values during the rainy season and higher values during the dry season, highlighting the impact of changes in moisture sources and local meteorological conditions on seasonal shifts in δD, δ18O, and δ17O. While, mean Δ′17O values were higher in rainy season and lower in dry season. Notably, during rainy season, there is a negative correlation between monthly Δ′17O values and the RH of the vapor source area, as well as a positive correlation with d‐excess. Recalculated Δ′17O values based on RH of oceanic moisture source, are higher than the measured values for this period, indicating the contribution of terrigenous moisture to precipitation in SW China. Precipitation Δ′17O values provide a more precise reflection of changes in moisture source, continental recycling, and evapotranspiration processes that drive water cycling compared Integrating modeling works in future will facilitate the use of precipitation Δ′17O values to quantify the impact of different moisture source on precipitation.

Testing triple oxygen isotope preservation in the new OPEnS totalizer against conventional monthly rainfall collectors

Understanding the mechanisms that drive spatial and temporal triple oxygen isotope (Δ′17O) variations in modern precipitation is the first step to expanding the utility of these measurements as an environmental tracer jointly with traditional stable isotope parameters δD, δ18O, and d-excess. However, “totalizers” designed to collect a single precipitation sample pooled over a calendar month and minimize evaporation and associated isotopic fractionation of the sample during that time have not been tested for Δ′17O. We conducted a 30-day laboratory experiment comparing mass losses and isotopic shifts in four totalizers: 1) the OPEnS (Openly Published Environmental Sensing) totalizer, 2) the classic oil-based totalizer, 3) the commercial tube dip-in/pressure equilibration totalizer (Palmex Ltd. RS1), and 4) a reference totalizer (the control, lacking any evaporation reduction mechanism). The OPEnS totalizer was designed as being readily user built with parts costs of about $10, oil-free to facilitate quick and easy sample preparation and risk-free sample analysis, and its collection device expands as it fills to maintain a small gas/water ratio and minimize internal evaporative losses. All totalizers were filled to 12 % of their 3-L volume and placed in a modified laboratory oven with a diurnal temperature change of 23 to 40 °C and an average relative humidity of 9.1 % to simulate extreme evaporative conditions. The OPEnS totalizer experienced the smallest mass loss of water (0.21 %) and smallest isotopic shifts (p < 0.05 for δ18O and d-excess), which were all within measurement error. The oil, tube, and reference totalizers showed larger mass losses (0.41, 1.37, and 1.61 %, respectively) and evaporative enrichment with respect to δD (+0.3, +0.8, and + 2.1 ‰), δ18O (+0.16, +0.23, and + 0.83 ‰), and d-excess (−0.9, −1.0, and − 4.5 ‰). The Δ′17O variations for all totalizers were within measurement error, so we suggest that in less harsh climates their triple oxygen isotope changes during secondary evaporation would be more acceptable. To test the OPEnS totalizer in field settings, we installed it alongside oil totalizers to collect monthly precipitation over three years in the towns of Jolly and San Antonio, Texas, with mean annual precipitation, temperature, and windspeed values of 556 and 563 mm, 18.7 and 21.9 °C, and 5.0 and 3.5 m/s, respectively. Results indicate that the OPEnS and oil totalizers can produce similar isotopic data in the field, but modifications to OPEnS have been implemented to minimize under-catch and stabilize the collection component where high winds are present and additional testing under a variety of environmental conditions is ongoing. OPEnS is scalable according to expected monthly precipitation amounts, providing a cost-effective, high-performance device for quantification of total rainfall and its isotopic composition without oil contamination risks.

Paleoaltimetry and paleotectonic reconstruction using triple oxygen and hydrogen isotopes: Depleted δ18O and δD values in ignimbrites of Verkhneavachinskaya caldera record collisional uplift during Miocene arc accretion to Kamchatka

Here we use δ18O and δD values as tools to investigate the paleo-altitude and the origin of large-volume (120 km3, 10 × 12 km) ignimbrites of Verkhneavachinskaya caldera (cf. Verkhne-Avachinskaya) (VC) in eastern Kamchatka, formed the in Late Miocene 5.8 Ma. The basaltic-andesitic intracaldera ignimbrite deposit exhibits low δ18O values, reaching −5.03‰, and δD values of −182‰ across a 1.2 km depth range in several sampled sections. The results support a massive meteoric-hydrothermal system throughout the cooling history of the thick intracaldera ignimbrite deposit. Using triple oxygen isotope data we estimate that the δ18O values of altering meteoric water are as low as −19‰ to −23‰, much lower than modern precipitation of −14‰, or − 16‰ estimated for the 2–3 °C warmer Kamchatka climate of the late Miocene. Therefore, the VC meteoric-hydrothermal system depended on high-altitude precipitation and glaciers, and altitudinal isotopic lapse rates suggest a paleo-altitude of 3.5 km at 5.8 Ma during caldera formation. These elevations exceed the modern by 1.5 km and provide a unique snapshot into an evolving landscape and paleo-environment of eastern Kamchatka at 6–5 Ma as the dynamic outcomes of accretion of the Kronotski arc. In particular, the existence of such a high plateau is in line with contemporary accretionary tectonics: accretion of the Shipunsky peninsula of this accreting arc terrain, ∼120 km to the east of the VC, and evidence of contemporaneous exhumation of high-grade Ganal amphibolites to the west. We conclude that the eruption of large-volume mafic ignimbrites that formed VC caldera was syncollisional or intracollisional in nature, likely requiring delamination of thickened crust to account for both uplift and magmatism.

Correcting for vital effects in coral carbonate using triple oxygen isotopes

Correcting for vital effects in coral carbonate using triple oxygen isotopes

Revealing the mechanisms of soil gypsum formation in the Atacama Desert through triple oxygen and hydrogen isotopes of gypsum hydration water

The soils in the hyper-arid core of the Atacama Desert (Chile) harbor substantial quantities of soluble salts, including sulfates and nitrates. Gypsum (CaSO₄∙2H₂O) is a prevalent mineral in the Atacama region. It manifests as ∼10-cm-thick surface crusts exhibiting a spatial pattern resembling polygons, in mixtures with other minerals beneath the surface (<3 m deep) or growing in brine ponds of salars. We examine the triple oxygen and hydrogen stable isotopes (δ17O, δ18O and δD) of structurally-bonded gypsum hydration water (GHW) from Atacama gypsum deposits to investigate their formation mechanisms. We observed considerably positive Δ17O anomalies (Δ17O > 1 ‰) in GHW of samples containing substantial amounts of nitrate (generally soil horizons 0.5–2 m deep). This is interpreted as resulting from oxygen isotope exchange between soil nitrate (Δ17O > 15 ‰) and GHW (Δ17O ∼ 0 ‰), either occurring in-situ within the soils due to bacterial activity, or more likely, during cryogenic extraction of GHW at high temperature and low pH in the laboratory. However, when analyzing pedogenic gypsum in soils with negligible amounts of nitrates, the isotopic composition of its parent solution is preserved. These samples showed that gypsum formed from solutions that did not undergo significant evaporation. These waters are isotopically similar to contemporary unevaporated freshwater sources in the region. This indicates that gypsum formation likely occurred through the hydration of anhydrous or hemihydrate calcium sulfate, either in the atmosphere or in the soil. Subsequently, the gypsum was subject to recrystallization in the soil due to occasional rainfall events. This stands in contrast to subaqueous gypsum crystals growing in brine ponds of salars in the Atacama Desert, which reflect the isotopic composition of highly-evaporated parent fluids.

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.

A tipping point in stable isotope composition of Antarctic meteoric waters during Cenozoic glaciation

Triple oxygen isotopes of Cenozoic intrusive rocks emplaced along the Ross Sea coastline in Antarctica, reveal that meteoric-hydrothermal waters imprinted their stable isotope composition on mineral phases, leaving a clear record of oxygen and hydrogen isotope variations during the establishment of the polar cap. Calculated O- and H-isotope compositions of meteoric waters vary from −9 ± 2‰ and −92 ± 5‰ at 40 ± 0.6 Ma, to −30 and −234 ± 5‰ at 34 ± 1.9 Ma, and intersect the modern Global Meteoric Water Line. These isotopic variations likely depict the combined variations in temperature, humidity, and moisture source regions, resulting from rearrangement of oceanic currents and atmospheric cooling during the onset of continental ice cap. Here, we report a paleo-climatic proxy based on triple oxygen geochemistry of crystalline rocks that reveals changes in the hydrological cycle. We discuss the magnitude of temperature changes at high latitudes during the Eocene-Oligocene climatic transition.

Precipitation 17O‐Excess Altered During Tropical Convection: Evidence From Monsoon Cold Surges in Singapore

AbstractDespite the recent recognition of 17O‐excess as a promising new tracer for hydrological processes, our knowledge of the control mechanisms underlying 17O‐excess in tropical regions remains limited. To understand how microphysical processes during tropical convection affect precipitation isotope ratios, particularly 17O‐excess, in Singapore, we collected precipitation samples at minute intervals from six rain events associated with cold surges during the Northeast Monsoon seasons and analyzed their triple oxygen isotopes. Our results show that precipitation δ18O decreases in the convective zones and then gradually increases in the stratiform zones, while d‐excess exhibits an inverse trend. This correlation between δ18O and d‐excess indicates that rain evaporation plays a crucial role in regulating precipitation isotopes. Moreover, the rain events with a higher upstream rainout amount have lower δ18O and higher 17O‐excess values, suggesting that precipitation δ18O and 17O‐excess likely reflect the integrated upstream convective activity. Microphysical processes associated with upstream convection, such as rain evaporation and vapor recycling, are potential mechanisms that increase 17O‐excess values along moisture transport pathways for a rain event, and hence, undermine the effectiveness of 17O‐excess as a tracer of moisture source humidity. Contrary to the negative correlation observed in monthly precipitation, there is generally a positive correlation between d‐excess and 17O‐excess at the event scale. However, this correlation weakens as convective rain intensifies, suggesting that stronger convection can attenuate the positive correlation between d‐excess and 17O‐excess. Therefore, it is crucial to consider how tropical convection alters 17O‐excess when utilizing this tracer to interpret atmospheric dynamics and hydrological processes.

Hydroclimate of the Messinian Salinity Crisis constrained from paleo-water triple oxygen, hydrogen, and strontium isotopes

Giant evaporite deposits formed during the Messinian Salinity Crisis (MSC) in the Mediterranean Sea during the upper Miocene. The primary cause is a restricted Atlantic-Mediterranean connection, but the detailed hydroclimate evolution of this event is still a matter of debate. Here we reconstruct the triple oxygen and hydrogen isotopic composition of paleo brines from structurally bonded water in Messinian gypsum from Cyprus. A two-stage evaporation model is constructed to best approximate the hydrological conditions at which Messinian gypsum formed in marginal basins of the Mediterranean Sea. Subsequently, hydroclimatic parameters like paleo relative humidity (RH) are modelled using an iterative curve fitting isotope model approach. The results of our limited dataset reveal a slightly lower RH during the third compared to the second stage of the MSC. This apparent drop in RH is consistent with previous observations from the literature.Besides absolute values of RH, our model allows reconstructing the triple oxygen and hydrogen isotopic composition of the open Mediterranean Sea. This provides an estimate for the proportions of continental water vs. Atlantic seawater flowing into the basin, serving as a proxy for the size of the strait of Gibraltar. The model implies a continental water fraction of around 75–81 % both for the second and third stage of the MSC. In addition, we determined the 87Sr/86Sr of our samples to: i) confirm their stratigraphy; and ii) estimate the relative proportion of continental water vs. Atlantic seawater entering the Mediterranean using Sr mass balance calculations. The combined oxygen and Sr isotope records indicate a persistent connection to the Atlantic supporting the hypothesis that the striking drop in 87Sr/86Sr at the beginning of MSC stage 3 is mainly related to an increased contribution of continental water with low 87Sr/86Sr and high Sr concentrations from the Paratethys. Our results show that the combination of triple oxygen, hydrogen, and Sr isotope data provides a powerful tool to disentangle paleo-hydroclimate even in such complicated hydrological settings as the Mediterranean Sea during the MSC.

Holocene Temperature and Water Stress in the Peruvian Andes: Insights From Lake Carbonate Clumped and Triple Oxygen Isotopes

AbstractGlobal climate during the Holocene was relatively stable compared to the late Pleistocene. However, evidence from lacustrine records in South America suggests that tropical latitudes experienced significant water balance variability during the Holocene, rather than quiescence. For example, a tight coupling between insolation and carbonate δ18O records from central Andean lakes (e.g., Lakes Junín, Pumacocha) suggest water balance is tied directly to South American summer monsoon (SASM) strength. However, lake carbonate δ18O records also incorporate information about temperature and evaporation. To overcome this ambiguity, clumped and triple oxygen isotope records can provide independent constraints on temperature and evaporation. Here, we use clumped and triple oxygen isotopes to develop Holocene temperature and evaporation records from three central Andean lakes, Lakes Junín, Pumacocha, and Mehcocha, to build a more complete picture of regional water balance (P–E). We find that Holocene water temperatures at all three lakes were stable and slightly warmer than during the latest Pleistocene. These results are consistent with global data assimilations and records from the foothills and Amazon basin. In contrast, evaporation was highly variable and tracks SASM intensity. The hydrologic response of each lake to SASM depends greatly on the physical characteristics of the lake basin, but they all record peak evaporation in the early to mid‐Holocene (11,700 to 4,200 years BP) when regional insolation was relatively low and the SASM was weak. These results corroborate other central Andean records and suggest synchronous, widespread water stress tracks insolation‐paced variability in SASM strength.

Triple oxygen isotope compositions reveal transitions in the moisture source of West China Autumn Precipitation

The isotopic composition has long been used to investigate the factors influencing precipitation, whereas the variations of event-based precipitation isotopes caused by moisture transition and synoptic meteorological conditions remain limited. Here we present triple oxygen and hydrogen isotopes in event-based precipitation during West China Autumn Precipitation to evaluate the influence of various moisture sources in the hydrological process. Isotopes δ18O, δ17O, and δD peak with convective precipitation at the onset stage, then drop to their lowest amid stratiform precipitation during the middle stage, and rise again towards the end. In contrast, Δ′17O levels remain elevated throughout the mid-stage of West China Autumn Precipitation compared to the onset and end stages. These isotopic variations, coupled with moisture analysis, reveal a distinct moisture source transition from the West Pacific Ocean to the westerly domain during West China Autumn Precipitation accompanied by the retreat of the Asian summer monsoon from Northwest China.

Triple isotopes (δD, δ18O, δ17O) characteristic of river water and groundwater in an arid watershed from Qaidam Basin, Northwestern China: implications for hydrological cycle

Combining traditional stable isotopes (δD and δ18O) and triple oxygen isotope (δ17O) is conducive to tracing hydrological cycle processes. The application of triple oxygen isotopes primarily focuses on precipitation, which is lacking in river water and groundwater. In this study, the spatial variations of δD, δ18O, δ17O, d-excess and 17O-excess of river water and groundwater in the Golmud River basin as well as the correlation between them were investigated to elucidate water origin and assess the evaporation influence on water bodies during flood season. Spatial changes in δD, δ18O and δ17O of river water exhibit a decrease-increase-stability pattern contrary to that observed for d-excess, 17O-excess has no distinct trend but is higher at both the source and downstream regions. The results show that river water and groundwater originate from precipitation in the mountainous area, and the meltwater in the source region also contribute to the river water with high d-excess and 17O-excess during flood season. The combination of d-excess and 17O-excess reveal that river water is also affected by evaporation and mixing of river water in tributaries. It was found that the river water is recharged in the mountains, undergoes evaporation in the upstream region and leaks into groundwater in the midstream region, which is recharged by the groundwater and evaporated again in the downstream region. This study could provide a more comprehensive understanding of the potential and value of triple oxygen isotopes in the hydrological cycle.

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.