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The short-lived 146Sm-142Nd isotope system traces key early planetary differentiation processes that occurred during the first 500 million-years of solar system history. The variations of 142Nd/144Nd in terrestrial samples, typically...
Reply to Comment on “190Pt-186Os geochronometer reveals open system behaviour of 190Pt-4He isotope system” by Yakubovich et al. (2022)
<p>A wide range of novel, non-traditional, stable isotope systems have been developed over the last decade, largely as a result of the advent of multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS), and continue to provide valuable new insights in the earth, environmental and planetary sciences. The platinum (Pt) stable isotope system represents a potentially powerful but, as yet, unexplored addition to this suite of stable isotope tracers. Pt has six naturally occurring isotopes, and can exist in a range of oxidation states. The geochemical behaviour of Pt coupled with the relatively large mass difference (ca. 2%) between the abundant heavy and light isotopes and its variable oxidation states leads to potential applications in tracing a range of natural processes. In particular, the strong elemental partitioning of Pt between metals and silicates makes the Pt stable isotope system uniquely suited to tracing processes of Earth’s accretion and differentiation. This study aims to develop new techniques for measurement of Pt stable isotopes in geological samples, and to apply these to terrestrial and meteorite samples to attempt to resolve outstanding questions relating to Earth’s early evolution. A technique was developed for measurement of Pt stable isotope ratios using multiple collector inductively coupled plasma mass spectrometry (MCICPMS), employing a ¹⁹⁶Pt–¹⁹⁸Pt double-spike to correct for instrumental mass fractionation. Results are reported in terms of δ¹⁹⁸Pt, which represents the per mil difference in the ¹⁹⁸Pt/¹⁹⁴Pt ratio from the IRMM-010 Pt isotope standard. A range of analytical tests were conducted and show that this approach has a reproducibility of ca. ±0.04 %∘ on δ¹⁹⁸Pt (i.e., ±0.01%∘ amu⁻¹) for Pt solution standards, and is insensitive to minor amounts of matrix that may be retained after chemical purification of Pt. Measurements of Pt solution standards conducted using two different MC-ICPMS instruments showed resolvable variations, which suggest that natural fractionations exist that exceed the reproducibility of the technique. Techniques were also developed for dissolution of natural samples and chemical separation of Pt. Geological standards were digested using a nickel sulphide fire assay technique, which pre-concentrates the highly siderophile elements in a NiS bead that is readily dissolved in acid. This was followed by chemical separation of Pt from digested samples using anion exchange chemical techniques. Elution curves were constructed for a range of synthetic rock matrices. These tests show that Pt separation is achieved with >90% Pt yield and ca. 95% purity. Analytical tests show that this level of Pt separation is sufficient for accurate determination of Pt stable isotope ratios by double-spike MC-ICPMS. These techniques were then applied to 11 international geological standard reference materials representing mantle peridotites, igneous samples, and Pt ore materials. The reproducibility in natural samples was determined by processing multiple replicate digestions of a standard reference material, and was shown to be ca. ±0.08%∘ (2 sd). Pt stable isotope data for the full set of reference materials have a range of δ¹⁹⁸Pt values with offsets of up to 0.40%∘ from the IRMM-010 standard, which are readily resolved with this technique. Mantle samples yielded the lightest (most negative) isotopic compositions of the terrestrial standards, with igneous and Pt ore samples defining a continuous trend towards zero, which is consistent with the IRMM-010 standard being derived from a Pt ore. These results demonstrate the potential of the Pt isotope system as a tracer in geochemical systems. The techniques developed above were then applied to investigate an outstanding problem relating to Earth’s accretion and differentiation. Highly siderophile elements (HSE) are strongly partitioned into the cores of terrestrial planets during core formation, and the abundances of HSE in Earth’s mantle compared with primitive meteorites have provided key constraints on models of Earth’s early evolution. Two leading models to explain the HSE abundances in the silicate Earth involve either a late-veneer of chondritic material that was added after core formation or core formation in a deep magma ocean. The platinum (Pt) stable isotope system represents a novel tool for investigating these processes. Using the techniques developed above, Pt stable isotope ratios were measured in a range of meteorite samples, including enstatite, ordinary and carbonaceous chondrites, primitive achondrites, achondrites and iron meteorites, as well as additional terrestrial mantle xenolith samples. Our data set reveals that the Pt stable isotopic composition of Earth’s mantle overlaps with all of the chondrite groups. Primitive achondrite and ureilite samples revealed the heaviest compositions of all meteorite groups. These data suggest that metal–silicate differentiation produces an isotopic fractionation for Pt, with heavy isotopes being preferentially retained in the silicate phase. Thus, Earth’s mantle is expected to have been significantly enriched in the heavy isotopes of Pt during core formation, even if metal–silicate differentiation took place in a magma ocean. The absence of a large fractionation between chondrites, representing the composition of the undifferentiated Earth, and the mantle suggests that the signature of core formation in the mantle has been subsequently overprinted. Considering the overlap between the Pt stable isotopic compositions of the mantle and chondrites, the most likely means for overprinting the composition of the mantle is by addition of a chondritic late-veneer. Mixing calculations show that addition of 0.5% of Earth’s mass by a late-veneer of chondritic material would be sufficient to overprint highly fractionated Pt stable isotope signatures resulting from core-formation.</p>
<p>A wide range of novel, non-traditional, stable isotope systems have been developed over the last decade, largely as a result of the advent of multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS), and continue to provide valuable new insights in the earth, environmental and planetary sciences. The platinum (Pt) stable isotope system represents a potentially powerful but, as yet, unexplored addition to this suite of stable isotope tracers. Pt has six naturally occurring isotopes, and can exist in a range of oxidation states. The geochemical behaviour of Pt coupled with the relatively large mass difference (ca. 2%) between the abundant heavy and light isotopes and its variable oxidation states leads to potential applications in tracing a range of natural processes. In particular, the strong elemental partitioning of Pt between metals and silicates makes the Pt stable isotope system uniquely suited to tracing processes of Earth’s accretion and differentiation. This study aims to develop new techniques for measurement of Pt stable isotopes in geological samples, and to apply these to terrestrial and meteorite samples to attempt to resolve outstanding questions relating to Earth’s early evolution. A technique was developed for measurement of Pt stable isotope ratios using multiple collector inductively coupled plasma mass spectrometry (MCICPMS), employing a ¹⁹⁶Pt–¹⁹⁸Pt double-spike to correct for instrumental mass fractionation. Results are reported in terms of δ¹⁹⁸Pt, which represents the per mil difference in the ¹⁹⁸Pt/¹⁹⁴Pt ratio from the IRMM-010 Pt isotope standard. A range of analytical tests were conducted and show that this approach has a reproducibility of ca. ±0.04 %∘ on δ¹⁹⁸Pt (i.e., ±0.01%∘ amu⁻¹) for Pt solution standards, and is insensitive to minor amounts of matrix that may be retained after chemical purification of Pt. Measurements of Pt solution standards conducted using two different MC-ICPMS instruments showed resolvable variations, which suggest that natural fractionations exist that exceed the reproducibility of the technique. Techniques were also developed for dissolution of natural samples and chemical separation of Pt. Geological standards were digested using a nickel sulphide fire assay technique, which pre-concentrates the highly siderophile elements in a NiS bead that is readily dissolved in acid. This was followed by chemical separation of Pt from digested samples using anion exchange chemical techniques. Elution curves were constructed for a range of synthetic rock matrices. These tests show that Pt separation is achieved with >90% Pt yield and ca. 95% purity. Analytical tests show that this level of Pt separation is sufficient for accurate determination of Pt stable isotope ratios by double-spike MC-ICPMS. These techniques were then applied to 11 international geological standard reference materials representing mantle peridotites, igneous samples, and Pt ore materials. The reproducibility in natural samples was determined by processing multiple replicate digestions of a standard reference material, and was shown to be ca. ±0.08%∘ (2 sd). Pt stable isotope data for the full set of reference materials have a range of δ¹⁹⁸Pt values with offsets of up to 0.40%∘ from the IRMM-010 standard, which are readily resolved with this technique. Mantle samples yielded the lightest (most negative) isotopic compositions of the terrestrial standards, with igneous and Pt ore samples defining a continuous trend towards zero, which is consistent with the IRMM-010 standard being derived from a Pt ore. These results demonstrate the potential of the Pt isotope system as a tracer in geochemical systems. The techniques developed above were then applied to investigate an outstanding problem relating to Earth’s accretion and differentiation. Highly siderophile elements (HSE) are strongly partitioned into the cores of terrestrial planets during core formation, and the abundances of HSE in Earth’s mantle compared with primitive meteorites have provided key constraints on models of Earth’s early evolution. Two leading models to explain the HSE abundances in the silicate Earth involve either a late-veneer of chondritic material that was added after core formation or core formation in a deep magma ocean. The platinum (Pt) stable isotope system represents a novel tool for investigating these processes. Using the techniques developed above, Pt stable isotope ratios were measured in a range of meteorite samples, including enstatite, ordinary and carbonaceous chondrites, primitive achondrites, achondrites and iron meteorites, as well as additional terrestrial mantle xenolith samples. Our data set reveals that the Pt stable isotopic composition of Earth’s mantle overlaps with all of the chondrite groups. Primitive achondrite and ureilite samples revealed the heaviest compositions of all meteorite groups. These data suggest that metal–silicate differentiation produces an isotopic fractionation for Pt, with heavy isotopes being preferentially retained in the silicate phase. Thus, Earth’s mantle is expected to have been significantly enriched in the heavy isotopes of Pt during core formation, even if metal–silicate differentiation took place in a magma ocean. The absence of a large fractionation between chondrites, representing the composition of the undifferentiated Earth, and the mantle suggests that the signature of core formation in the mantle has been subsequently overprinted. Considering the overlap between the Pt stable isotopic compositions of the mantle and chondrites, the most likely means for overprinting the composition of the mantle is by addition of a chondritic late-veneer. Mixing calculations show that addition of 0.5% of Earth’s mass by a late-veneer of chondritic material would be sufficient to overprint highly fractionated Pt stable isotope signatures resulting from core-formation.</p>
<p>Understanding the eruptive history of a volcanically active region is critical in assessing the hazard and risk posed by future eruptions. In regions where surface deposits are poorly preserved, and ambiguously sourced, tephrostratigraphy is a powerful tool to assess the characteristics of past eruptions. The city of Auckland, New Zealand’s largest urban centre and home to ca. 1.4 million people, is built on top of the active Auckland Volcanic Field (AVF). The AVF is an intraplate monogenetic basaltic volcanic field, with ca. 53 eruptive centres located in an area of ca. 360 km2. Little is known however, about the evolution of the field because the numerical and relative ages of the eruptions are only loosely constrained, and therefore the precise order of many eruptions is unknown. Here I apply tephrostratigraphic and geochemical techniques to investigate the chronology and magmatic evolution of the AVF eruptions. First, I present an improved methodology for in-situ analysis of lacustrine maar cores from the AVF by employing magnetic susceptibility and X-ray density scanning on intact cores. These techniques are coupled with geochemical microanalysis of the tephra-derived glass shards to reveal details of reworking within the cores. These details not only allow assessment of the deposit relationships within cores (e.g. primary vs. reworked horizons), but also to correlate tephra horizons between cores. Through the correlation of tephra units across cores from a variety of locations across the field, an improved regional tephrostratigraphic framework for the AVF deposits has been established. Following on from this, I detail the methods developed in this study to correlate tephra horizons within the maar cores back to their eruptive source. This technique uses geochemical fingerprinting to link the glass analyses from tephra samples to whole rock compositions. Such an approach has not been previously attempted due to the complications caused by fractional crystallisation, which affects concentrations of certain key elements in whole rock analyses. My method resolves these issues by using incompatible trace elements, which are preferentially retained in melt over crystals, and therefore retain comparable concentrations and concentration ratios between these two types of sample. Because of the primitive nature of the AVF magmas, their trace element signature is largely controlled by the involvement of several distinct mantle sources. This leads to significant variability between the volcanic centres that thus can be used for individually fingerprinting, and correlating tephra to whole rocks. Nevertheless, in some cases geochemistry cannot provide an unambiguous correlation, and a multifaceted approach is required to allow the correlation of the tephra horizons to source. The other criteria used to correlate tephra deposits to their source centre include, Ar-Ar ages of the centres, modelled and calculated ages of the tephra deposits, the scale of eruption, and the deposit locations and thicknesses. The results of this research outline the methodology for assessing occurrence and characteristics of basaltic tephra horizons within lacustrine maar cores, and the methodology for correlating these horizons to their eruptive source. In doing this the relative eruption order of the AVF is accurately determined for the first time. Temporal trends suggest acceleration of eruption repose periods to 21 ka followed by deceleration to present. Although no spatial evolution is observed, coupling of some centres is seen when spatial and temporal evolution are combined. The geochemical signature of the magmas appears to evolve in a cyclic manner with time, incorporating increasing amount of a shallow source. This evolution is seen both during a single eruption sequence and throughout the lifespan of the AVF. Finally, pre-eruptive processes are assessed as part of the study of the magmatic evolution of the AVF. The effects of contamination from the crust and lithosphere through which the magma ascends are evaluated using the Re-Os isotope system. The results show there are variable inputs from crustal sources, which have previously not been identified by traditional isotope systems (e.g. Pb-Sr-Nd isotopes). Two sources of contamination are identified based on their Os systematics relating to two terranes beneath the AVF: the metasedimentary crust and the Dun Mountain Ophiolite Belt. The identification of this process suggests there is interaction of ascending melt with the crust, contrary to what previous studies have concluded. This body of research has provided a detailed reconstruction of the chronostratigraphy and magmatic evolution of the AVF to aid accurate and detailed risk assessment of the threat posed by a future eruption from the Auckland Volcanic Field.</p>
<p>Understanding the eruptive history of a volcanically active region is critical in assessing the hazard and risk posed by future eruptions. In regions where surface deposits are poorly preserved, and ambiguously sourced, tephrostratigraphy is a powerful tool to assess the characteristics of past eruptions. The city of Auckland, New Zealand’s largest urban centre and home to ca. 1.4 million people, is built on top of the active Auckland Volcanic Field (AVF). The AVF is an intraplate monogenetic basaltic volcanic field, with ca. 53 eruptive centres located in an area of ca. 360 km2. Little is known however, about the evolution of the field because the numerical and relative ages of the eruptions are only loosely constrained, and therefore the precise order of many eruptions is unknown. Here I apply tephrostratigraphic and geochemical techniques to investigate the chronology and magmatic evolution of the AVF eruptions. First, I present an improved methodology for in-situ analysis of lacustrine maar cores from the AVF by employing magnetic susceptibility and X-ray density scanning on intact cores. These techniques are coupled with geochemical microanalysis of the tephra-derived glass shards to reveal details of reworking within the cores. These details not only allow assessment of the deposit relationships within cores (e.g. primary vs. reworked horizons), but also to correlate tephra horizons between cores. Through the correlation of tephra units across cores from a variety of locations across the field, an improved regional tephrostratigraphic framework for the AVF deposits has been established. Following on from this, I detail the methods developed in this study to correlate tephra horizons within the maar cores back to their eruptive source. This technique uses geochemical fingerprinting to link the glass analyses from tephra samples to whole rock compositions. Such an approach has not been previously attempted due to the complications caused by fractional crystallisation, which affects concentrations of certain key elements in whole rock analyses. My method resolves these issues by using incompatible trace elements, which are preferentially retained in melt over crystals, and therefore retain comparable concentrations and concentration ratios between these two types of sample. Because of the primitive nature of the AVF magmas, their trace element signature is largely controlled by the involvement of several distinct mantle sources. This leads to significant variability between the volcanic centres that thus can be used for individually fingerprinting, and correlating tephra to whole rocks. Nevertheless, in some cases geochemistry cannot provide an unambiguous correlation, and a multifaceted approach is required to allow the correlation of the tephra horizons to source. The other criteria used to correlate tephra deposits to their source centre include, Ar-Ar ages of the centres, modelled and calculated ages of the tephra deposits, the scale of eruption, and the deposit locations and thicknesses. The results of this research outline the methodology for assessing occurrence and characteristics of basaltic tephra horizons within lacustrine maar cores, and the methodology for correlating these horizons to their eruptive source. In doing this the relative eruption order of the AVF is accurately determined for the first time. Temporal trends suggest acceleration of eruption repose periods to 21 ka followed by deceleration to present. Although no spatial evolution is observed, coupling of some centres is seen when spatial and temporal evolution are combined. The geochemical signature of the magmas appears to evolve in a cyclic manner with time, incorporating increasing amount of a shallow source. This evolution is seen both during a single eruption sequence and throughout the lifespan of the AVF. Finally, pre-eruptive processes are assessed as part of the study of the magmatic evolution of the AVF. The effects of contamination from the crust and lithosphere through which the magma ascends are evaluated using the Re-Os isotope system. The results show there are variable inputs from crustal sources, which have previously not been identified by traditional isotope systems (e.g. Pb-Sr-Nd isotopes). Two sources of contamination are identified based on their Os systematics relating to two terranes beneath the AVF: the metasedimentary crust and the Dun Mountain Ophiolite Belt. The identification of this process suggests there is interaction of ascending melt with the crust, contrary to what previous studies have concluded. This body of research has provided a detailed reconstruction of the chronostratigraphy and magmatic evolution of the AVF to aid accurate and detailed risk assessment of the threat posed by a future eruption from the Auckland Volcanic Field.</p>
Research subject. The Sm/Nd isotope system was investigated using inter-laboratory natural samples of apatite, titanite, allanite, monazite, as well as intra-laboratory samples of apatite (from carbonatites, Ilmenogorsk massif, Ural), monazite (from pegmatites of the Aduy granite massif and its framing, Middle Urals) and titanite (from calcite veins, Saranov skoye chromite deposit, Middle Urals and from alkaline pegmatite, Shpat mine, Vishnevy mountains, South Urals). The Sr isotope system was investigated using inter-laboratory natural apatite samples and intra-laboratory apatite samples (from the apatite-carbonate vein, Slyudyanogorskoe deposit, Irkutsk region and from carbonatites, Ilmenogorsk massif, Ural).Methods. The research was carried using a Neptune Plus multicollector mass spectrometer with inductively coupled plasma (ThermoFisher) equipped with an NWR 213 (ESI) laser ablation attachment, located in a room of ISO class 7 at the “Geoanalyst” Center for Collective Use (IGG Ural Branch of the Russian Academy of Sciences, Ekaterinburg). Results. The article describes methodological approaches for studying Sm/Nd and Sr isotope systems in natural phosphate and silicate minerals by inductively coupled plasma mass spectrometry with laser ablation, implemented on the equipment of the Center for Collective Use “Geoanalyst” (IGG Ural Branch of the Russian Academy of Sciences, Ekaterinburg). A comparative analysis of the obtained results with those reported in literature showed their satisfactory agreement. The developed analytical approaches were used to study apatite samples (analysis of the Sr isotope system) and those of apatite, monazite, titanite (analysis of the Sr isotope system). Conclusions. The developed approaches to the analysis of Sm/Nd and Sr isotopic systems can be recommended for investigating such minerals, as apatite, titanite, allanite, monazite (analysis of the Sm/Nd isotope system); apatite (analysis of the Sr isotope system). The achieved analysis errors allow the results to be used for interpreting various geochemical processes.
Abstract —In the northern Ladoga area, the age of the Sortavala Group rocks in the southeast of the Raahe–Ladoga zone of junction of the epi-Archean Fenno-Karelian Craton and the Paleoproterozoic Svecofennian province, their relationship with dome granitoids, the age of the provenances, and the time of metamorphic processes were estimated. The study was focused on the Nd isotope composition of rocks, the geochemical and isotope-geochronological parameters of zircon from the granite-gneisses of the Kirjavalakhti dome, the basal graywackes of the lower unit and the trachytes of the middle unit of the Sortavala Group, and the plagio- and diorite-porphyry dikes cutting the volcanosedimentary units of this group. The new isotope-geochemical data show a Neoarchean age of the granitoids of the Kirjavalakhti dome (2695 ± 13 Ma) and their juvenile nature (εNd(T) = +1.5). The granitoids underwent tectonometamorphic transformations (rheomorphism) in the Paleoproterozoic (Sumian) (2.50–2.45 Ga), which are recorded in the U–Th–Pb isotope system of the rims of the ancient cores of zircon crystals. The volcanosedimentary complex of the Sortavala Group formed on the heterogeneous polychronous (3.10–2.46 Ga) continental crust of the epi-Archean Fenno-Karelian Craton. With regard to the errors in determination of the age of clastic zircon, the minimum concordant U–Th–Pb ages of 1940–1990 Ma of detrital zircon from volcanomictic graywackes of the Pitkyaranta Formation can be taken as the upper age bound of terrigenous rocks, which agrees with the maximum age of the Sortavala Group rocks estimated from the U–Th–Pb (SIMS) age of 1922 ± 11 Ma of the Tervaoya diorites (Matrenichev et al., 2006). According to the proposed new tectonic model, the accumulation of the volcanosedimentary complex of the Sortavala Group, its metamorphism, erosion, and overlapping by the Ladoga Group turbidites had already occurred in the pericratonic part of the epi-Archean Fenno-Karelian Craton by the time of the Svecofennian continent–island arc collision, subduction, and formation of bimodal volcanoplutonic complexes of the young Pyhäsalmi island arcs and felsic volcanics of the Savo schist belt (1920–1890 Ma).
ABSTRACT Different types of sediment-hosted whole-rock Pb isotope (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb) compositions were determined from phyllites, carbonaceous phyllites (>1% TOC), and meta-litharenites belonging to the Serra do Garrote Formation, which is part of the Proterozoic Vazante Group, Brazil. Results were integrated with lithogeochemistry in order to identify the Pb isotopic signature of Zn enrichment (up to 0.24 wt.% Zn) associated with meta-siliciclastic-hosted sulfide mineralization that formed prior to the Brasiliano Orogeny (850 to 550 Ma) in order to (1) understand the nature of siliciclastic sediment sources, (2) identify possible metal sources in pre-orogenic meta-siliciclastic-hosted Zn mineralization, and (3) evaluate the genetic links between the Zn enrichment in the relatively reduced phyllite package, and different styles of syn-orogenic Zn ± Pb mineralization (hypogene Zn-silicate and Zn-Pb sulfide) in overlying dolomitic carbonates throughout the Vazante-Paracatu Zn District, Brazil. The whole-rock 206Pb/204Pb and 207Pb/204Pb isotope ratios of meta-siliciclastic rocks plot as positively sloping, sub-parallel arrays with radiogenic, upper continental crust compositions, which could represent a detrital contribution from at least two upper continental crust sources. However, the 206Pb/204Pb versus 207Pb/204Pb isotope system does not distinguish between Zn-enriched samples and un-mineralized samples. In the whole-rock 206Pb/204Pb–208Pb/204Pb plot, Zn-enriched samples form a flat trend of lower 208Pb/204Pb values (38.3 to 39.5) compared to the Zn-poor ones that follow common upper crustal trends. Zinc-enriched samples have low whole-rock Th/U values (<4) and higher whole-rock U concentrations compared to unmineralized samples. These support the hypothesis that U (± Pb) was added by pre-orogenic metalliferous fluids, which were in turn derived from underlying Paleoproterozoic and Archean basement rocks. Due to U addition, the original whole-rock thorogenic and uranogenic Pb isotope systems were decoupled in mineralized samples. Pre-orogenic metalliferous fluids have similar present-day first-order characteristics, including: (1) relatively high U/Pb and (2) low Th/U values, when compared to galena in the major carbonate-hosted Zn ± Pb deposits (Vazante, Morro Agudo, Ambrosia, Fagundes) in the Vazante Group. These results support the hypothesis that Zn-rich layers and veins in mineralized carbonaceous phyllites could be linked to the same origins as carbonate-hosted mineral deposits throughout the Vazante Basin, but further data are warranted. We suggest that the tectonic evolution of the Vazante Basin saw multiple phases of Zn-rich mineralization over protracted time periods from around 1200 to 550 Ma.
Abstract. This paper presents an extension of the scientific HDO/H2O column data product from the Tropospheric Monitoring Instrument (TROPOMI) including clear-sky and cloudy scenes. The retrieval employs a forward model which accounts for scattering, and the algorithm infers the trace gas column information, surface properties and effective cloud parameters from the observations. The extension to cloudy scenes greatly enhances coverage, particularly enabling data over oceans. The data set is validated against co-located ground-based Fourier transform infrared (FTIR) observations by the Total Carbon Column Observing Network (TCCON). The median bias for clear-sky scenes is 1.4 × 1021 molec cm−2 (2.9 %) in H2O columns and 1.1 × 1017 molec cm−2 (−0.3 %) in HDO columns, which corresponds to −17 ‰ (9.9 %) in a posteriori δD. The bias for cloudy scenes is 4.9 × 1021 molec cm−2 (11 %) in H2O, 1.1 × 1017 molec cm−2 (7.9 %) in HDO, and −20 ‰ (9.7 %) in a posteriori δD. At low-altitude stations in low and middle latitudes the bias is small, and has a larger value at high latitude stations. At high altitude stations, an altitude correction is required to compensate for different partial columns seen by the station and the satellite. The bias in a posteriori δD after altitude correction depends on sensitivity due to shielding by clouds, and on realistic prior profile shapes for both isotopologues. Cloudy scenes generally involve low sensitivity below the clouds, and since the information is filled up by the prior, it plays an important role in these cases. Over oceans, aircraft measurements with the Water Isotope System for Precipitation and Entrainment Research (WISPER) instrument from a field campaign in 2018 are used for validation, yielding a bias of −3.9 % in H2O and −3 ‰ in δD over clouds. To demonstrate the added value of the new data set, a short case study of a cold air outbreak over the Atlantic Ocean in January 2020 is presented, showing the daily evolution of the event with single overpass results.
