Fractionation of O₂∕N₂ and Ar∕N₂ in the Antarctic ice sheet during bubble formation and bubble–clathrate hydrate transition from precise gas measurements of the Dome Fuji ice core

The variations of δO2/N2 and δAr/N2 in the Dome Fuji ice core were measured from 112 m (bubbly ice) to 2001 m (clathrate hydrate ice). Our method, combined with the low storage temperature of the samples (−50 ∘C), successfully excludes post-coring gas-loss fractionation signals from our data. From the bubbly ice to the middle of the bubble–clathrate transition zone (BCTZ) (112–800 m) and below the BCTZ (>1200 m), the δO2/N2 and δAr/N2 data exhibit orbital-scale variations similar to local summer insolation. The data in the lower BCTZ (800–1200 m) have large scatter, which may be caused by millimeter-scale inhomogeneity of air composition combined with finite sample lengths. The insolation signal originally recorded at the bubble close-off remains through the BCTZ, and the insolation signal may be reconstructed by analyzing long ice samples (more than 50 cm for the Dome Fuji core). In the clathrate hydrate zone, the scatter around the orbital-scale variability decreases with depth, indicating diffusive smoothing of δO2/N2 and δAr/N2. A simple gas diffusion model was used to reproduce the smoothing and thus constrain their permeation coefficients. The relationship between δAr/N2 and δO2/N2 is markedly different for the datasets representing bubble close-off (slope ∼ 0.5), bubble–clathrate hydrate transformation (∼1), and post-coring gas loss (∼0.2), suggesting that the contributions of the mass-independent and mass-dependent fractionation processes are different for those cases. The method and data presented here may be useful for improving the orbital dating of deep ice cores over the multiple glacial cycles and further studying non-insolation-driven signals (e.g., atmospheric composition) of these gases.

Volcanic origin of the mercury anomalies at the Cretaceous-Paleogene transition of Bidart, France

The timing and mechanisms of the climatic and environmental perturbations induced by the emplacement of the Deccan Traps large igneous province (India) and their contribution to the Cretaceous-Paleogene (K-Pg) mass extinction are still debated. In many marine sediment archives, mercury (Hg) enrichments straddling the K-Pg boundary have been interpreted as the signature of Deccan Traps volcanism, but Hg may also have been derived from the Chicxulub (Mexico) impact. We investigated the Hg isotope composition, as well as the behavior of iridium (Ir) and other trace elements, in K-Pg sediments from the Bidart section in southwest France. Above the K-Pg boundary, Ir content gradually decreases to background values in the Danian carbonates, which is interpreted to indicate the erosion and redistribution of Ir-rich fallouts. No significant enrichment in Ir and W, or Zn and Cu, is observed just below the K-Pg boundary, excluding the hypothesis of downward remobilization of Hg from the boundary clay layer. Positive Δ199Hg and slightly negative values in the upper Maastrichtian and lower part of the early Danian are consistent with the signature of sediments supplied by atmospheric Hg2+ deposition and volcanic emissions. Up section, large shifts to strongly negative mass-dependent fractionation values (δ202Hg) result from the remobilization of Hg formerly sourced by the impactor or by a mixture of different sources including biomass burning, volcanic eruption, and asteroid impact, requiring further investigation. Our results provide additional support for the interpretation that the largest eruptions of the Deccan Traps began just before, and encompassed, the K-Pg boundary and therefore may have contributed to the K-Pg mass extinction.

Fractionation of O₂/N₂ and Ar/N₂ in the Antarctic ice sheet during bubble formation and bubble-clathrate hydrate transition from precise gas measurements of the Dome Fuji ice core

The variations of δO2/N2 and δAr/N2 in the Dome Fuji ice core were measured from 112 m (bubbly ice) to 2001 m (clathrate hydrate ice) at high precision. Our method, combined with the low storage temperature of the samples (−50 °C), successfully excludes post-coring gas-loss fractionation signals from our data. From the bubbly ice to the middle of the bubble-clathrate transition zone (BCTZ) (112–800 m) and below the BCTZ (> 1200 m), the δO2/N2 and δAr/N2 data exhibit orbital-scale variations similar to local summer insolation. The data in the lower BCTZ (800–1200 m) have large scatters, which may be caused by mm-scale inhomogeneity of air composition combined with finite sample lengths. The insolation signal originally recorded at the bubble close-off remains through the BCTZ, and the insolation signal may be reconstructed by analyzing long ice samples. In the clathrate hydrate zone, the scatters around the orbital-scale variability decrease with depth, indicating diffusive smoothing of δO2/N2 and δAr/N2. A simple gas diffusion model was used to reproduce the smoothing and thus constrain their permeation coefficients. The relationship between δAr/Ν2 and δO2/N2 is markedly different for the datasets representing bubble close-off (slope ~0.5), bubble-clathrate hydrate transformation (~1), and post-coring gas-loss (~0.2), suggesting that the contribution of the mass-independent and mass-dependent fractionation processes are different for those cases. The method and data presented here may be useful for improving the orbital dating of deep ice cores over the multiple glacial cycles and further studying non-insolation-driven signals (e.g., atmospheric composition) of these gases.

Industrially Purified Nd Materials Identified by Distinct Mass-Dependent Isotopic Composition

Rare earth elements (REEs) are considered emerging anthropogenic pollutants. Anthropogenic lanthanum, cerium, samarium, and gadolinium alone, or excess of all the REEs have already been reported in the environment. In addition, it is only a matter of time for neodymium (Nd) of anthropogenic origin to be reported disseminated in the environment, given its growing demand for new technologies and its use in permanent magnets of wind turbine. So far, only in a few cases was the addition of anthropogenic Nd detected in soils and sediments by the measurements of REE concentrations. For this reason, we propose to use the Nd isotopic composition to help the distinction of pollution. The isotopic tracing of Nd using variations in the abundance of 143Nd from the radioactive decay of 147Sm (Nd-radiogenic composition) is one option. Here, we expand the Nd isotopic fingerprinting by the investigation of the stable Nd isotopic composition expressed as δxNd, the relative permil (%0) deviation from the isotopic composition of the pure Nd JNdi-1 reference standard. The measurement of δxNd used a MC-ICPMS (multi-collector inductively coupled plasma mass spectrometry) with sample-standard bracketing technique, allowing the determination of precise and accurate Nd isotopic variations. Our results show that Nd-magnets (Neo) and man-made purified Nd materials are not significantly different on average (respectively, δ148Nd of −0.105 ± 0.023 and −0.120 ± 0.141%0). More importantly, they are different from terrestrial rocks (δ148Nd of −0.051 ± 0.031%0). Moreover, the Nd-radiogenic composition of Neo can be highly variable, even when they come from a single supplier. In addition, the study of all Nd stable isotopic compositions demonstrates that irrespective of their natural origin (witnessed by their Nd-radiogenic composition), all Nd from rocks and man-made materials are related by mass-dependent isotopic fractionation laws. We also have defined a parameter, the Δ148−150Nd′, allowing the distinction of thermodynamic isotopic fractionation (the Δ148−150Nd′ is invariant) from kinetic isotopic fractionation (the Δ148−150Nd′ is negatively correlated with the δ148Nd). Such covariation is observed for anthropogenic materials that could be seen as small deficit in 150Nd (around 5 ppm/%0/amu), but too small to be consistent with nuclear field effect. On the other hand, the anthropogenic material defines a covariation in the Δ148−150Nd'–δ148Nd space in full agreement with the theoretical expectation from mass-dependent kinetic isotopic fractionation. The mass-dependent fractionation of Nd by chromatographic separation is also consistent with a kinetic isotopic fractionation. The purification of Nd from other light REEs by industrial processes involves chromatographic separation and, therefore, is likely to produce anthropogenic Nd with low values for δ148Nd associated with high values for Δ148−150Nd′. Both are resolvable with current MC-ICPMS technology and could be useful to trace incoming anthropogenic pollution in the environment. In soils, the combination of low values for δ148Nd with high values for Δ148−150Nd′ is likely to be an unambiguous pollution signal from the degradation in the environment of Neo or other industrial products, especially if this is associated with an Nd-radiogenic composition inconsistent with the surrounding rocks and soils. In contrast, the industrial residue of Nd purification could be characterized by high δ148Nd with low values for Δ148−150Nd′, and the leak or the discharge of such residue could also be unambiguously distinguished.

Long-term observations of δ13C-CO2, δ18O-CO2, δ17O-CO2 and “excess” 17O-CO2 by Quantum Cascade Dual-Laser Absorption Spectrometry in whole air flask samples from Lutjewad station, the Netherlands

<p>We present long-term results of δ<sup>13</sup>C-CO<sub>2</sub>, δ<sup>18</sup>O-CO<sub>2</sub>, δ<sup>17</sup>O-CO<sub>2 </sub>and “excess” <sup>17</sup>O-CO<sub>2 </sub>or Δ<sup>17</sup>O-CO<sub>2 </sub>measurements in whole air flask samples collected at Lutjewad monitoring station in the Netherlands using an Aerodyne Quantum Cascade Dual-Laser Spectrometer system (QCDLAS). The station is located at the Dutch Wadden sea coast (6.353°E, 53.404°N) in a rural environment. The flask samples have been collected at 60 m altitude at a bi-weekly rate, spanning from July 2016 until the end of 2020. The location of Lutjewad station allows to measure clean marine background air from the north-northwest (~15% of the time) in contrast to continental air from a prevalent south-westerly direction (~50% of the time). Our observations include the summers of 2018 and 2019 which saw exceptionally hot and dry conditions in large parts of Europe, including the Netherlands.</p><p>The Δ<sup>17</sup>O-CO<sub>2 </sub>anomaly is defined as the deviation from normal mass dependent fractionation reflected in CO<sub>2 </sub>equilibrated with water, occurring over water bodies, but mainly in plant leaves. Atmospheric Δ<sup>17</sup>O-CO<sub>2 </sub>has been used as a parameter to study gross primary production (GPP), notably as a function of water availability. Here, the determination of Δ<sup>17</sup>O-CO<sub>2 </sub>is derived from the direct measurement of δ<sup>17</sup>O-CO<sub>2 </sub>next to δ<sup>18</sup>O-CO<sub>2 </sub>(Δ<sup>17</sup>O = ln(δ<sup>17</sup>O +1)-0.5229×ln(δ<sup>18</sup>O +1)). Using the summer 2018 and 2019 results we investigate the potential of using the Δ<sup>17</sup>O-CO<sub>2 </sub>signal derived from QCDLAS measurements from Lutjewad as a tracer for suppressed plant assimilation due to water stress.</p>

Stable Ca and Sr isotopes support volcanically triggered biocalcification crisis during Oceanic Anoxic Event 1a

Large igneous province (LIP) eruptions are hypothesized to trigger biocalcification crises. The Aptian nannoconid crisis, which correlates with emplacement of the Ontong Java Plateau and Oceanic Anoxic Event 1a (OAE 1a, ca. 120 Ma), represents one such example. The Ca isotope (δ44/40Ca) system offers potential to detect biocalcification fluctuations in the rock record because Ca isotope fractionation is sensitive to precipitation rate. However, other primary and secondary processes, such as input-output flux perturbations and early diagenesis, can produce similar signals. Here, we exploit emergent properties of the stable Sr isotope (δ88/86Sr) system to resolve the origin of δ44/40Ca variability during OAE 1a. This study reports high-precision thermal ionization mass spectrometry (TIMS) δ44/40Ca, δ88/86Sr, and 87Sr/86Sr records for Hole 866A of Ocean Drilling Program Leg 143 drilled in Resolution Guyot, mid-Pacific Ocean. The samples span ~27 m.y. from the Barremian (ca. 127 Ma) to the Albian (ca. 100 Ma). The δ44/40Ca and δ88/86Sr secular trends differ from the 87Sr/86Sr record but mimic each other. δ44/40Ca and [Sr], as well as δ44/40Ca and δ88/86Sr, strongly correlate and yield slopes predicted for kinetic control, which demonstrates that variable mass-dependent fractionation rather than end-member mixing dominated the isotopic relationship between carbonates and seawater. Positive δ44/40Ca and δ88/86Sr shifts that begin before OAE 1a and peak within the interval are consistent with reduced precipitation rates. All results combined point to a cascade of effects on rate-dependent Ca and Sr isotope fractionation, which derive from the dynamic interplay between LIP eruptions and biocalcification feedbacks.

Common physiological processes control mercury reduction during photosynthesis and fermentation

ABSTRACTMercury (Hg) is a global pollutant and potent neurotoxin that bioaccumulates in food webs as monomethylmercury (MeHg). The production of MeHg is driven by anaerobic and Hg redox cycling pathways such as Hg reduction, which control the availability of Hg to methylators. Anaerobes play an important role in Hg reduction in methylation hotspots, yet their contributions remain underappreciated due to how challenging these pathways are to study in the absence of dedicated genetic targets and low levels of Hg0 in anoxic environments. In this study we used Hg stable isotope fractionation to explore Hg reduction during anoxygenic photosynthesis and fermentation in the model anaerobe Heliobacterium modesticaldum Ice1. We show that cells preferentially reduce lighter Hg isotopes in both metabolisms leading to mass-dependent fractionation, but mass-independent fractionation commonly induced by UV-visible light is absent. We show that isotope fractionation is affected by the interplay between pathways controlling Hg recruitment, accessibility, and availability alongside metabolic redox reactions. The combined contributions of these processes lead to isotopic enrichment during anoxygenic photosynthesis that is in between the values reported for anaerobic respiratory microbial Hg reduction and abiotic photoreduction. Isotope enrichment during fermentation is closer to what has been observed in aerobic bacteria that reduce Hg through dedicated detoxification pathways. These results demonstrate that common controls exist at the atomic level for Hg reduction during photosynthesis and fermentation in H. modesticaldum. Our work suggests that similar controls likely underpin diverse microbe-mediated Hg transformations that affect Hg’s fate in oxic and anoxic habitats.IMPORTANCEAnaerobic and photosynthetic bacteria that reduce mercury affect mercury delivery to microbes in methylation sites that drive bioaccumulation in food webs. Anaerobic mercury reduction pathways remain underappreciated in the current view of the global mercury cycle because they are challenging to study, bearing no dedicated genetic targets to establish physiological mechanisms. In this study we used stable isotopes to show that common physiological processes control mercury reduction during photosynthesis and fermentation in the model anaerobe Heliobacterium modesticaldum Ice1. The sensitivity of isotope analyses highlighted the subtle contribution of mercury uptake towards the isotope signature associated with anaerobic mercury reduction. When considered alongside the isotope signatures associated with microbial pathways for which genetic determinants have been identified, our findings underscore the narrow range of isotope enrichment that is characteristic of microbial mercury transformations. This suggests that there exist common atomic-level controls for biological mercury transformations across a broad range of geochemical conditions.

Seeds of Life in Space (SOLIS)

Context. Contrary to what is expected from models of Galactic chemical evolution, the isotopic fractionation of silicon (Si) in the Galaxy has recently been found to be constant. This finding calls for new observations, also at core scales, to re-evaluate the fractionation of Si. Aims. L1157-B1 is one of the outflow-shocked regions along the blue-shifted outflow that is driven by the Class 0 protostar L1157-mm. It is an ideal laboratory for studying the material ejected from the grains on very short timescales because its chemical composition is representative of the composition of the grains. Methods. We imaged 28SiO, 29SiO, and 30SiO J = 2–1 emission towards L1157-B1 and B0 with the NOrthern Extended Millimeter Array (NOEMA) interferometer as part of the Seeds of Life in Space (SOLIS) large project. We present here a study of the isotopic fractionation of SiO towards L1157-B1. Furthermore, we used the high spectral resolution observations on the main isotopologue, 28SiO, to study the jet impact on the dense gas. We here also present single-dish observations obtained with the IRAM 30 m telescope and Herschel-HIFI. We carried out a non-local thermal equilibrium analysis using a large velocity gradient code to model the single-dish observations. Results. From our observations we can show that (i) the 2–1 transition of the main isotopologue is optically thick in L1157-B1 even at high velocities, and (ii) the [29SiO/30SiO] ratio is constant across the source, and consistent with the solar value of 1.5. Conclusions. We report the first isotopic fractionation maps of SiO in a shocked region and show the absence of a mass-dependent fractionation in 29Si and 30Si across L1157-B1. A high-velocity bullet in 28SiO has been identified, showing the signature of a jet impacting on the dense gas. With the dataset presented in this paper, both interferometric and single-dish, we were able to study the gas that is shocked at the B1a position and its surrounding gas in great detail.

The Great Oxidation Event preceded a Paleoproterozoic “snowball Earth”

The inability to resolve the exact temporal relationship between two pivotal events in Earth history, the Paleoproterozoic Great Oxidation Event (GOE) and the first “snowball Earth” global glaciation, has precluded assessing causality between changing atmospheric composition and ancient climate change. Here we present temporally resolved quadruple sulfur isotope measurements (δ34S, ∆33S, and ∆36S) from the Paleoproterozoic Seidorechka and Polisarka Sedimentary Formations on the Fennoscandian Shield, northwest Russia, that address this issue. Sulfides in the former preserve evidence of mass-independent fractionation of sulfur isotopes (S-MIF) falling within uncertainty of the Archean reference array with a ∆36S/∆33S slope of −1.8 and have small negative ∆33S values, whereas in the latter mass-dependent fractionation of sulfur isotopes (S-MDF) is evident, with a ∆36S/∆33S slope of −8.8. These trends, combined with geochronological constraints, place the S-MIF/S-MDF transition, the key indicator of the GOE, between 2,501.5 ± 1.7 Ma and 2,434 ± 6.6 Ma. These are the tightest temporal and stratigraphic constraints yet for the S-MIF/S-MDF transition and show that its timing in Fennoscandia is consistent with the S-MIF/S-MDF transition in North America and South Africa. Further, the glacigenic part of the Polisarka Formation occurs 60 m above the sedimentary succession containing S-MDF signals. Hence, our findings confirm unambiguously that the S-MIF/S-MDF transition preceded the Paleoproterozoic snowball Earth. Resolution of this temporal relationship constrains cause-and-effect drivers of Earth’s oxygenation, specifically ruling out conceptual models in which global glaciation precedes or causes the evolution of oxygenic photosynthesis.