Isotopic Anomalies Research Articles

Triple Oxygen and Clumped Isotope Compositions of CO2 in the Middle Troposphere

AbstractWe report the oxygen isotopic anomaly (Δ17O) and clumped isotopic composition (Δ47) of CO2 sampled from the middle troposphere (~10 km above ground) during two CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) flights in summer and winter seasons: one from Düsseldorf to Isla Margarita on 11 August 2001 and the other from Puerto Plata to Munich on 21 February 2002. The mid‐tropospheric Δ17O values were higher than the near‐surface values by 0.051 ± 0.010 ‰, indicating enhanced stratospheric influence. The Δ47 values were also higher by 0.160 ± 0.015 ‰ compared to that from the lower troposphere. Stratospheric influence is supported by the observed correlations of the Δ17O values with the mixing ratios of N2O, O3, and 14CO, which carry stratospheric signatures. The increase in the anomaly in the free troposphere represents a balance between the stratosphere‐troposphere exchange fluxes and biogeochemical/hydrospheric isotopic resetting rates at the Earth surface. Using a simple two box model with the free tropospheric Δ17O values, an average surface exchange rate of CO2 between 327 and 772 PgC/year is inferred, giving a CO2 turnover time of 1.4 to 2.8 years in the atmosphere. The present estimates are based on a rather small set of free tropospheric data and have relatively large uncertainties, but they agree with the existing model and proxy‐based estimates.

Hydrogen isotopic anomalies in extraterrestrial organic matter: role of cosmic ray irradiation and implications for UCAMMs

Context. Micrometeorites represent, at timescales shorter than a few million years, the dominant source of extraterrestrial matter at the surface of the Earth. Analyses of ultracarbonaceous micrometeorites recovered from Antarctica, known as UCAMMs reveal an exceptionally N-rich organic matter associated with spatially extended high D enrichments. Experiments show that this specific organic matter might have been formed in the outer solar system by energetic irradiation of N-rich icy surfaces. Aims. We experimentally investigate the hydrogen isotopic fractionation resulting from irradiation of normal and D-rich N2-CH4 ices by high energy ions, simulating the exposition to Galactic cosmic rays of icy bodies surfaces orbiting at large heliocentric distances. Methods. Films of N2-CH4 ices and a N2-CH4/CD4/N2-CH4 “sandwich” ice were exposed to 129Xe13+ ion beams at 92 and 88 MeV. The chemical evolution of the samples was monitored using in situ Fourier transform infrared spectroscopy. After irradiation, targets were annealed to room temperature. The solid residues of the whole process left after ice sublimation were characterized in situ by infrared spectroscopy, and the hydrogen isotopic composition measured ex situ by imaging secondary ion mass spectrometry at the sub-micron scale (NanoSIMS). Results. Irradiation leads to the formation of new molecules and radicals. After annealing, the resulting poly-HCN-like macro-molecular residue exhibits an infrared spectrum close to that of UCAMMs. The residue resulting from irradiation of N2-CH4 ices does not exhibit a significant deuterium enrichment comparable to that found in extraterrestrial organic matter. The residue formed by irradiation of D-rich ices shows the formation of isotopic heterogeneities with localised hotspots and an extended contribution likely due to the diffusion of the radiolytic products from the D-rich layer. Conclusions. These results show that high-energy cosmic ray irradiation does not induce the large hydrogen isotopic fractionation observed at small spatial scale in interplanetary organics. By contrast, large D/H ratio heterogeneities at the sub-micron spatial scale in extraterrestrial organic matter can result from isotopically heterogeneous ices mixtures (i.e. condensed with different D/H ratios), which were transformed into refractory organic matter upon irradiation.

Post-spreading Basalts from the Nanyue Seamount: Implications for the Involvement of Crustal- and Plume-Type Components in the Genesis of the South China Sea Mantle

Fresh samples of basalts were collected by dredging from the Nanyue intraplate seamount in the Southwest sub-basin of the South China Sea (SCS). These are alkali basalts displaying right-sloping, chondrite-normalized rare earth element (REE) profiles. The investigated basalts are characterized by low Os content (60.37–85.13 ppt) and radiogenic 187Os/188Os ratios (~0.19 to 0.21). Furthermore, 40Ar/39Ar dating of the Nanyue basalts showed they formed during the Tortonian (~8.3 Ma) and, thus, are products of (Late Cenozoic) post-spreading volcanism. The Sr–Nd–Pb–Hf isotopic compositions of the Nanyue basalts indicate that their parental melts were derived from an upper mantle reservoir possessing the so-called Dupal isotopic anomaly. Semiquantitative isotopic modeling demonstrates that the isotopic compositions of the Nanyue basalts can be reproduced by mixing three components: the average Pacific midocean ridge basalt (MORB), the lower continental crust (LCC), and the average Hainan ocean island basalt (OIB). Our preferred hypothesis for the genesis of the Nanyue basalts is that their parental magmas were produced from an originally depleted mantle (DM) source that was much affected by the activity of the Hainan plume. Initially, the Hainan diapir caused a thermal perturbation in the upper mantle under the present-day Southwest sub-basin of the SCS that led to erosion of the overlying LCC. Eventually, the resultant suboceanic lithospheric mantle (SOLM) interacted with OIB-type components derived from the nearby Hainan plume. Collectively, these processes contributed crustal- and plume-type components to the upper mantle underlying the Southwest sub-basin of the SCS. This implies that the Dupal isotopic signature in the upper mantle beneath the SCS was an artifact of in situ geological processes rather than a feature inherited from a Southern Hemispheric, upper mantle source.

Heavy oxygen recycled into the lithospheric mantle

Magmas in volcanic arcs have geochemical and isotopic signatures that can be related to mantle metasomatism due to fluids and melts released by the down-going oceanic crust and overlying sediments, which modify the chemistry and mineralogy of the mantle wedge. However, the effectiveness of subduction-related metasomatic processes is difficult to evaluate because the composition of arc magmas is often overprinted by interactions with crustal lithologies occurring during magma ascent and emplacement. Here, we show unequivocal evidence for recycling of continental crust components into the mantle. Veined peridotite xenoliths sampled from Tallante monogenetic volcanoes in the Betic Cordillera (southern Spain) provide insights for mantle domains that reacted with Si-rich melts derived by partial melting of subducted crustal material. Felsic veins crosscutting peridotite and the surrounding orthopyroxene-rich metasomatic aureoles show the highest 18O/16O ratios measured to date in upper mantle assemblages worldwide. The anomalously high oxygen isotope compositions, coupled with very high 87Sr/86Sr values, imply the continental crust origin of the injected melts. Isotopic anomalies are progressively attenuated in peridotite away from the veins, showing 18O isotope variations well correlated with the amount of newly formed orthopyroxene. Diffusion may also affect the isotope ratios of mantle rocks undergoing crustal metasomatism due to the relaxation of 18O isotope anomalies to normal mantle values through time. Overall, the data define an O isotope “benchmark” allowing discrimination between mantle sources that attained re-equilibration after metasomatism (>5 Myr) and those affected by more recent subduction-derived enrichment processes.

Triple oxygen isotopic evidence for atmospheric nitrate and its application in source identification for river systems in the Qinghai-Tibetan Plateau

Nitrate source identification in river systems is important for water quality management. Recently, the oxygen isotopic anomaly of nitrate in atmospheric deposition (Δ17Oatm) is used to identify unprocessed atmospheric nitrate in river systems to reduce the uncertainty caused by the wide range of δ18O. In high-elevation regions, such as the Qinghai-Tibetan Plateau (QTP) featured with lower temperature and pressure as well as strong radiation, the Δ17Oatm might be different from that in low-elevation regions, but no relevant studies have been reported. In this work, Δ17Oatm in the QTP was studied, and the fingerprints of nitrate isotopes in synthetic fertilizer, livestock manure, domestic sewage, and soil organic nitrogen (SON) were identified and used to quantify various source contributions to riverine nitrate in the Yellow River and Changjiang River source regions located in the QTP during 2016–2017. The results showed that the average of Δ17Oatm in the QTP was 16.4‰, lower than the range (19–30‰) reported for the low-elevation regions. The possible mechanism is decreased O3 as well as increased hydroxyl and peroxy radical levels in the troposphere caused by the climate condition and ozone valley in the QTP will affect the production pathways of atmospheric nitrate. By combining the sewage discharge data with the output results of the SIAR (stable isotope analysis in R) model based on the stable isotope data, manure was determined to be one of the major sources to riverine nitrate for both rivers. The contributions of various sources to riverine nitrate were 47 ± 10% for manure, 30 ± 5% for SON, 10 ± 4% for atmospheric precipitation, 9 ± 2% for synthetic fertilizer, and 4 ± 0% for sewage in the Yellow River source region. This study indicates that the unique atmospheric conditions in the QTP have led to a lower Δ17Oatm value, and atmospheric source makes a considerable contribution to riverine nitrate in the QTP.

Sequence stratigraphy and chemostratigraphy of an Ediacaran-Cambrian foreland-related carbonate ramp (Bambuí Group, Brazil)

In the terminal Neoproterozoic, drastic climate changes associated with biological innovations are coupled to isotope and elemental geochemical anomalies. However, lateral variability and local depositional controls may affect global geochemical signals, which can only be tracked through a proper stratigraphic/paleogeographic assessment. Here, we investigate the sequence stratigraphy and chemostratigraphy of the basal units of the Bambuí Group, central-east Brazil. This stratigraphic unit records a foreland basin system developed during the Ediacaran-Cambrian West Gondwana assembly and represents a 1st-order sequence, in which the two lowermost 2nd-order sequences record major geochemical disturbances. The first 2nd-order sequence started with the deposition of a transgresive systems tract, possibly in a postglacial scenario, which accompanies a negative-to-positive δ13Ccarb excursion. The early highstand systems tract represents the establishment of a marine carbonate ramp throughout the basin. In terms of chemostratigraphy, it corresponds to a δ13Ccarb plateau close to 0‰ and Sr/Ca ratios around 0.001. The late highstand stage coincides with a remarkable increase in Sr content and Sr/Ca ratios at basinal scale. Occurrences of the Cloudina sp. late Ediacaran index fossil were reported in this stage. An erosional unconformity associated with a dolomitic interval, locally including subaerial exposure features, marks the top of the first 2nd-order sequence. This sequence boundary heralds an abrupt increase in δ13Ccarb values, up to +14‰. These extremely high δ13Ccarb values and high Sr/Ca ratios persist throughout the overlying sequence, as a result of progressive and enhanced restriction of the foreland basin system. Basin restriction at this stage has implications for the paleontological and chemostratigraphic record of epicontinental basins of the West Gondwana in the terminal Ediacaran. Late Ediacaran Sr-rich intervals in these basins show unusually non-radiogenic 87Sr/86Sr ratios, which may represent local depositional controls and deviations from the modern oceanographic models. Physiographic barriers and stressful conditions likely represented extreme environments for metazoan colonization.

Identification of Large Isotope Anomalies in Quartz by Infrared Spectroscopy.

We report an infrared (IR) spectroscopic technique to detect quartz grains with large isotope anomalies. We synthesized isotopically doped quartz and used Fourier transform infrared spectroscopy (FT-IR) in two different instruments: a traditional far-field instrument and a neaSpec nanoFT-IR, to quantify the shift in the peak of the Si-O stretch near 780 cm-1 as a function of isotope composition, and the uncertainty in this shift. From these measurements, we estimated the minimum detectable isotope anomaly using FT-IR. The described technique can be used to nondestructively detect very small (30 nm) presolar grains. In particular, supernova grains, which can have very large isotope anomalies, are detectable by this method.

Uniform 182W isotope compositions in Eoarchean rocks from the Isua region, SW Greenland: The role of early silicate differentiation and missing late veneer

Abstract Eoarchean rocks from the Isua region in southern West Greenland are known to exhibit isotope anomalies of 182W and 142Nd. The excess 182W in many rocks from the Isua region have been explained by two endmember models: (1) missing late veneer or (2) silicate differentiation shortly after Earth’s formation. Furthermore, it has been proposed that pristine W isotope systematics in rocks from the Isua region (herein the Isua supracrustal belt and adjacent area) have been obscured by metamorphic disturbance. To address these issues, we present a comprehensive dataset, combining high precision 182W isotope data with trace element data, including high precision elemental W-Th-U-Ta abundance data. We present an improved analytical protocol that allows processing gram-sized samples with W abundances in the lower ng/g range. This protocol also results in markedly improved ion exchange column yields and cleaner W fractions, thereby minimizing nuclear volume effects on 183W. To compare with previous studies, our dataset includes some samples from previously investigated units in the Isua region (Isua Supracrustal Belt (ISB) mafic–ultramafic assemblages and Ameralik dikes). In addition, several Eoarchean key units in the Isukasia terrane (Isua region) and the Faeringehavn terrane (Nuuk region) have been examined for their W isotope composition in this study for the first time. These newly investigated units include recently recognized mantle-like peridotites from both terranes that display PGE abundances and patterns similar to modern depleted mantle peridotites, felsic lithologies from the ISB, as well as key amphibolite and TTG localities from low-strain domains south of the ISB. Virtually all rocks from the Isua region show significant W enrichment with W/Th of up to 160 in mafic to ultramafic samples. None of the samples from SW Greenland that were object of 182W isotope analysis in this study and virtually all previous studies appear to have preserved near canonical W/Th ratios (i.e., between 0.09 and 0.24). Independent of W enrichment, however, it can now be shown that there is a uniform 182W isotope excess in the different rock types from the Itsaq Gneiss Complex (IGC) (average 12.8 ppm ± 1 ppm, 95% confidence interval). Importantly, none of the rock suites investigated exhibit modern mantle-like 182W isotope signatures of µ182W = 0. By combining 182W signatures in the different lithologies with elemental W systematics, we therefore can infer that the 182W excess in Eoarchean rocks from the Isua region is widespread, and independent of W enrichment. Hence, we regard the 182W excess as an intrinsic feature of the Eoarchean assemblages in the Isua region. Notably, mantle-like peridotites from both the Isukasia and Faeringehavn terranes display the same 182W excess, as all other units, although they have been shown to display the full inventory of Highly Siderophile Elements (HSE) found in Phanerozoic mantle peridotites. Evidently, the W isotope budget in these rocks is clearly decoupled from HSE systematics, which hampers a straightforward explanation for 182W isotope excesses in terms of the missing late veneer model. As Platinum Group Element (PGE) patterns in mantle-like Eoarchean peridotites from the Isua region are similar to those in Phanerozoic rocks, we rather propose that to a large extent the 182W excesses are a vestige of early silicate differentiation processes, in line with positive 142Nd anomalies found in rocks from the Isua region, suggesting initial silicate differentiation prior to 4.50 Ga.

Calcareous nannoplankton proxies for palaeoenvironmental reconstruction of the Albian–Cenomanian succession in North-western Israel (Mount Carmel Region)

Abstract We present data on the calcareous nannofossil distribution in the Albian–Cenomanian borehole CT8 obtained from the Carmel area, NW Israel. The nannofloral assemblage consists of 113 species, with Watznaueria spp. dominating the entire succession. The detailed calcareous nannofossil biostratigraphy of this section is established, and seven nannofossil (sub)zones are recognised. For the first time the age of the Tavasim Tuff (V2) is biostratigraphically identified as Late Albian. The quantitative analysis of the calcareous nannofossils suggests warm, open marine or coastal, mainly oligotrophic conditions throughout the entire succession of borehole CT8, with evident fluctuations of temperatures and fertility and a general trend towards cooling in the uppermost part of the sequence (Middle–Late Cenomanian). Temperature and nutrient variations correspond to those in the western Tethys, thus suggesting at least a supra-regional extent of processes detected in the Carmel Region. The biostratigraphy shows no evidence of hiatuses in the studied section, but the absence of positive carbon isotope anomalies associated with the Oceanic Anoxic Event (OAE) 1d and Mid-Cenomanian Event elsewhere suggests that the OAE 1d is possibly missing in the studied section due to a hiatus around the Isfiye Fm./Arqan Fm. boundary.

Tracing the Deep Carbon Cycle Using Metal Stable Isotopes: Opportunities and Challenges

Abstract The subduction of marine carbonates and carbonated oceanic crust to the Earth’s interior and the return of recycled carbon to the surface via volcanism may play a pivotal role in governing Earth’s atmosphere, climate, and biosphere over geologic time. Identifying recycled marine carbonates and evaluating their fluxes in Earth’s mantle are essential in order to obtain a complete understanding of the global deep carbon cycle (DCC). Here, we review recent advances in tracing the DCC using stable isotopes of divalent metals such as calcium (Ca), magnesium (Mg), and zinc (Zn). The three isotope systematics show great capability as tracers due to appreciable isotope differences between marine carbonate and the terrestrial mantle. Recent studies have observed anomalies of Ca, Mg, and Zn isotopes in basalts worldwide, which have been interpreted as evidence for the recycling of carbonates into the mantle, even into the mantle transition zone (410–660 km). Nevertheless, considerable challenges in determining the DCC remain because other processes can potentially fractionate isotopes in the same direction as expected for carbonate recycling; these processes include partial melting, recycling of carbonated eclogite, separation of metals and carbon, and diffusion. Discriminating between these effects has become a key issue in the study of the DCC and must be considered when interpreting any isotope anomaly of mantle-derived rocks. An ongoing evaluation on the plausibility of potential mechanisms and possible solutions for these challenges is discussed in detail in this work. Based on a comprehensive evaluation, we conclude that the large-scale Mg and Zn isotope anomalies of the Eastern China basalts were produced by recycling of Mg- and Zn-rich carbonates into their mantle source.

A sensitive λ 3 mm line survey of L483: A broad view of the chemical composition of a core around a Class 0 object.

An exhaustive chemical characterization of dense cores is mandatory to our understanding of chemical composition changes from a starless to a protostellar stage. However, only a few sources have had their molecular composition characterized in detail. Here we present a λ 3 mm line survey of L483, a dense core around a Class 0 protostar, which was observed with the IRAM 30m telescope in the 80-116 GHz frequency range. We detected 71 molecules (140 including different isotopologs), most of which are present in the cold and quiescent ambient cloud according to their narrow lines (FWHM ~0.5 km s-1) and low rotational temperatures (≲10 K). Of particular interest among the detected molecules are the cis isomer of HCOOH, the complex organic molecules HCOOCH3, CH3OCH3, and C2H5OH, a wide variety of carbon chains, nitrogen oxides like N2O, and saturated molecules like CH3SH, in addition to eight new interstellar molecules (HCCO, HCS, HSC, NCCNH+, CNCN, NCO, H2NCO+, and NS+) whose detection has already been reported. In general, fractional molecular abundances in L483 are systematically lower than in TMC-1 (especially for carbon chains), tend to be higher than in L1544 and B1-b, and are similar to those in L1527. Apart from the overabundance of carbon chains in TMC-1, we find that L483 does not have a marked chemical differentiation with respect to starless/prestellar cores like TMC-1 and L1544, although it does chemically differentiate from Class 0 hot corino sources like IRAS 16293-2422. This fact suggests that the chemical composition of the ambient cloud of some Class 0 sources could be largely inherited from the dark cloud starless/prestellar phase. We explore the use of potential chemical evolutionary indicators, such as the HNCO/C3S, SO2/C2S, and CH3SH/C2S ratios, to trace the prestellar/protostellar transition. We also derived isotopic ratios for a variety of molecules, many of which show isotopic ratios close to the values for the local interstellar medium (remarkably all those involving 34S and 33S), while there are also several isotopic anomalies like an extreme depletion in 13C for one of the two isotopologs of c-C3H2, a drastic enrichment in 18O for SO and HNCO (SO being also largely enriched in 17O), and different abundances for the two 13C substituted species of C2H and the two 15N substituted species of N2H+. We report the first detection in space of some minor isotopologs like c-C3D. The exhaustive chemical characterization of L483 presented here, together with similar studies of other prestellar and protostellar sources, should allow us to identify the main factors that regulate the chemical composition of cores along the process of formation of low-mass protostars.

Carbon isotope minima in the South Atlantic during the last deglaciation: evaluating the influence of air-sea gas exchange

Carbon isotope minima were a ubiquitous feature in the mid-depth (1.5–2.5 km) Atlantic during Heinrich Stadial 1 (HS1, 14.5–17.5 kyr BP) and the Younger Dryas (YD, 11.6–12.9 kyr BP), with the most likely driver being collapse of the Atlantic Meridional Overturning Circulation (AMOC). Negative carbon isotope anomalies also occurred throughout the surface ocean and atmosphere, but their timing relative to AMOC collapse and the underlying drivers have remained unclear. Here we evaluate the lead-lag relationship between AMOC variability and surface ocean δ13C signals using high resolution benthic and planktonic stable isotope records from two Brazil Margin cores (located at 1.8 km and 2.1 km water depth). In each case, the decrease in benthic δ13C during HS1 leads planktonic δ13C by 800 ± 200 years. Because the records are based on the same samples, the relative timing is constrained by the core stratigraphy. Our results imply that AMOC collapse initiates a chain of events that propagates through the oceanic carbon cycle in less than 1 kyr. Direct comparison of planktonic foraminiferal and atmospheric records implies a portion of the surface ocean δ13C signal can be explained by temperature-dependent equilibration with a 13C-depleted atmosphere, with the remainder due to biological productivity, input of carbon from the abyss, or reduced air-sea equilibration.

Fingerprints of the protosolar cloud collapse in the Solar System: Refractory inclusions distribution and isotopic anomalies in meteorites

AbstractIncreasing evidences suggest that the building blocks of Ca-Al-rich inclusions (CAIs) could have formed with the Sun, during the collapse of the parent cloud. However, determination of the relative age of CAIs relies on the homogeneous distribution of their short-lived radionuclide 26Al that is used as a chronometer. Some CAIs show evidence of 26Al/27 Al variation that is independent of decay.We investigate the dynamical and chemical evolution of refractories from the collapsing cloud to their transport in the protoplanetary disk focusing to the predicted isotopic anomalies resulting from 26Al heterogeneities.The interplay between the thermal properties of the dust, the isotopic zoning in the cloud and disk dynamics produce aggregates that resemble chondrites. An abrupt raise of 26Al close the center of the cloud followed by a plateau throughout the cloud best matches the observations. As a consequence, the 26Al -chronometer retains validity from the formation of canonical CAIs onward.

Titanium isotopic evidence for a shared genetic heritage of refractory inclusions from different carbonaceous chondrites

Abstract Insights into the earliest stages of our Solar System can be derived from its oldest dated solids, calcium-aluminum-rich inclusions (CAIs). In particular, investigating isotopic anomalies of nucleosynthetic origin in CAIs offers potential clues to the genetic heritage of refractory inclusions and the reservoir(s) involved in their formation. To this point, however, nucleosynthetic anomalies in refractory inclusions have almost exclusively been recognized in (1) relatively large CAIs from CV3 chondrites, employing chemical purification and high-precision mass spectrometry, or (2) from sub-mm-sized hibonite-rich objects (e.g., PLACs, SHIBs) from the Murchison CM2 chondrite using much less precise in-situ techniques. Whereas the latter have been shown to be highly anomalous in their isotopic compositions, their genetic connection to ‘regular’ CAIs from carbonaceous chondrites remains poorly understood. Here, we aim to address this issue by taking advantage of a new technique that allows for high-precision analysis of sub-mm-sized inclusions. Using this method, we report Ti isotope anomalies in a suite of twelve CAIs from five different CO carbonaceous chondrites, as well as ten refractory inclusions from the CM2 chondrite Jbilet Winselwan using MC-ICPMS. We find that these CO and CM CAIs exhibit Ti isotopic compositions very similar to those of previously investigated CV3 (and of two CK3) CAIs, suggesting a fundamental genetic relationship of CAIs found within these chondrite groups. As such, our data indicates that CAIs from various groups of carbonaceous chondrites formed from similar matter and in a single region of the solar nebula (i.e., derived from a single common CAI-formation region). Collectively, these data show evidence of large-scale transport of CAIs over a significant range of heliocentric distances, covering at least the accretion areas of the CV, CK, CO, and CM chondrites. In addition, we report two inclusions consisting of hibonite-rich crystal aggregates from Jbilet Winselwan that exhibit highly irregular nucleosynthetic Ti signatures, implying a distinct origin from the aforementioned CAIs. These inclusions may represent an earlier generation of refractory material, perhaps more akin to the previously mentioned PLACs and/or SHIBs.

THE LOWER BAJOCIAN GAETANI LEVEL: LITHOSTRATIGRAPHIC MARKER OF A POTENTIAL OCEANIC ANOXIC EVENT

In this paper we document in detail the transition from the Rosso Ammonitico Lombardo to the Radiolarites outcropping at Alpe Turati (Albavilla, Como) in the Lombardy Basin of the Southern Alps. At this location, the Jurassic succession was deposited on a flank of the Corni di Canzo paleohigh: as found on other structural shallow areas, the upper Pliensbachian–Toarcian–Aalenian interval is represented by pseudonodular to nodular marly limestones of the Morbio Limestone and Rosso Ammonitico Lombardo units. In the early Bajocian deposition of biosiliceous sediments is ubiquitously testified by the Radiolarites (Bajocian–Callovian). At Alpe Turati, the interval immediately below the basal green member of the latter unit, consists of a 10 cm thick black shale, pointing to oxygen-depleted bottom waters. Dysoxia persisted during the Bajocian–Callovian as evidenced by dark green stratified cherts. Calcareous nannofossil biostratigraphy indicate an early Bajocian age for the black shale that correlates with the core of a distinct C isotopic negative anomaly also known in various basins outside the Southern Alps. Very dark grey to black lithologies of early Bajocian age have been documented in a few sections from Poland, Corsica and Morocco. We name Gaetani Level the black shale interval in recognition of Maurizio Gaetani’s pioneering and extensive work on Jurassic sedimentary successions of the Lombardy Basin. The association of the Gaetani black shale with a C isotopic anomaly suggests that it could be the sedimentary record of an Oceanic Anoxic Event whose regional to global extension must be ascertained.

Oxygen isotopes in HED meteorites and their constraints on parent asteroids

The howardite, eucrite and diogenite (HED) clan of meteorites are usually regarded as Vesta meteorites, but there is still serious controversy over whether Vesta is the only parent body for HEDs. Different numbers of HED parent asteroids have been proposed in previous studies of oxygen isotopes. The main controversy is whether the anomalous oxygen isotopic compositions in some HEDs are caused by factors such as terrestrial weathering, addition of exogenous material during brecciation, or a possible primary isotopic heterogeneity of Vesta. To readdress the questions of whether all HED meteorites are from the same parent body, or to constrain the possible number of multiple parent asteroids, the oxygen isotopic data of 166 HED meteorites from the literature are compiled and reviewed here. Among them, 146 HED meteorites have similar Δ17O values of −0.240 ± 0.020‰ (2σ), and the remaining 20 meteorites show oxygen isotopic anomalies (Δ17O values fall outside 3σ from the above mean). Fifteen HED meteorites have anomalous oxygen isotope compositions that cannot be accounted for by terrestrial weathering or the addition of exogenous material, while the oxygen isotope anomalies in the remaining 5 HEDs are caused by the above factors. Based on studies of a number of isotopic and trace element systems, HED meteorites should form from a magma ocean, thus their parent asteroid is highly likely to be homogeneous. This implies that the oxygen isotope variability of HEDs suggest multiple parent bodies for these meteorites, which is supported by arguments from astrophysical and other geochemical studies such as Zn and Cr. In summary, according to the Δ17O values and a number of other observations, we believe that HED meteorites most likely originate from at least 6 different basaltic asteroids.

Quantitative models for the elemental and isotopic fractionations in chondrites: The carbonaceous chondrites

Abstract A quantitative understanding of the elemental and isotopic fractionations recorded in the compositions of the chondritic meteorites would provide fundamental constraints for astrophysical models of early Solar System evolution. Here it is shown through least squares fitting that almost all features of the bulk elemental and isotopic compositions of the main carbonaceous chondrite (CC) groups, as well as the ungrouped Tagish Lake (C2) meteorite, can be reproduced using mixtures of the same four components. The fractionations amongst the non-CCs (ordinary, Rumuruti and enstatite chondrites) are distinctly different to those in the CCs and are the subject of a separate study (Alexander, 2019). The four CC components are: (1) a ‘chondrule’ (or chondrule precursor) component that partially lost Fe,Ni metal and volatiles, but is otherwise CI-like, (2) the cc -RI component that has a refractory inclusion-like bulk composition and is largely responsible for the refractory element enrichments and nucleosynthetic isotope anomalies in the bulk CCs, (3) anhydrous and reduced but otherwise CI-like matrix that accounts for almost all of the most volatile element (e.g., Zn, Se and C) contents of the CCs, and (4) water with relatively high Δ17O and δ18O values. Comparison of the inferred component compositions to additional meteoritic constraints produces some notable results. The e48Ca ≈ 8 and e50Ti ≈ 8 values for the cc -RI component are consistent with the average values for refractory inclusions. On the other hand, the e54Cr ≈ −10 is not, but is required by the negative correlation between e50Ti and e54Cr amongst the bulk CCs. The cc -RI component may be comprised of a more CAI-like sub-component that carries the e48Ca and e50Ti anomalies, and a more ferromagnesian sub-component that carries the negative e54Cr anomalies. The compositions of the volatile and metal subcomponents lost from the ‘chondrule’ component are consistent with condensation models, suggesting that the fractionations predated chondrule formation. The isotopic compositions of chondrules from the more cc -RI-rich CC groups (e.g., CV, CO and CM) seem to require the addition of some of the cc -RI component to their precursors. The assumption that matrix is CI-like is inconsistent with chondrule-matrix complementarity, but is justified by the success of the fits and the relatively uniform and CI-like abundances of organics and presolar grains in the matrices of the most primitive CCs. The inferred Δ17O = 3.5‰ for the water component is consistent with most constraints from secondary phases in the CCs. The large O isotopic mass fractionation (δ18O ≈ 18–21‰) of the water is consistent with ∼89–95% condensation of ice from a vapor under Rayleigh conditions at 150–170 K. The water was entirely accreted with the matrix with fairly constant (0.32 ± 0.06 by wt.) and CI-like (∼0.38 by wt.) water/matrix ratios. These water/matrix ratios are much less than the water/rock ratio of one that is often cited for a nebula of solar composition, but can be explained if much of the C in the CC formation regions was present as CO and CO2, and the abundance of CH4 was low.

Petrological, mineralogical and geochemical peculiarities of Archaean cratons

The most outstanding features of Archaean cratons are their extraordinary thickness and enduring longevity. Seismically, Archaean cratonic fragments are sharply-bounded deep roots of mechanically strong, cold lithospheric mantle, clearly distinguishable from non-cratonic lithosphere. Rhenium-depletion of deep cratonic xenolith whole rocks and sulphide inclusions in diamond indicate that melting was broadly coeval with formation of the overlying proto-cratonic crust, which was of limited mechanical strength.A very important process of proto-cratonic development was vertical crustal reorganisation that eventually yielded a thermally stable, cratonised crust with a highly K-U-Th-rich uppermost crust and much more depleted deeper crust. Clastic sedimentary rocks available for geochemical study are predominantly found in the youngest parts of supracrustal stratigraphies and over-represent the highly evolved rocks that appeared during cratonisation. Vertical crustal reorganisation was driven by crustal radiogenic heat and emplacement of proto-craton-wide, incubating and dense supracrustal mafic and ultramafic volcanic rocks. Statistical analysis of these cover sequences shows a preponderance of basalt and a high abundance of ultramafic lavas with a dearth of picrite. The ultramafic lavas can be grouped into Ti-enriched and Ti-depleted types and high pressure and temperature experimental data indicate that the latter formed from previously depleted mantle at temperatures in excess of 1700 °C.Most mantle harzburgite xenoliths from cratonic roots are highly refractory, containing very magnesian olivine and many have a high modal abundance of orthopyroxene. High orthopyroxene mode is commonly attributed to metasomatic silica-enrichment or a non-pyrolitic mantle source but much of the excess silica requirement disappears if melting occurred at high pressures of 4–6 GPa. Analysis of experimental data demonstrates that melting of previously depleted harzburgite can yield liquids with highly variable Si/Mg ratios and low Al2O3 and FeO contents, as found in komatiites, and complementary high Cr/Al residues. In many harzburgites, there is an intimate spatial association of garnet and spinel with orthopyroxene, which indicates formation of the Al-phase by exsolution upon cooling and decompression. New and published rare earth element (REE) data for garnet and orthopyroxene show that garnet has inherited its sinusoidal REE pattern from the orthopyroxene. The lack of middle-REE depletion in these refractory residues is consistent with the lack of middle- over heavy-REE fractionation in most komatiites. This suggests that such pyroxene or garnet (or precursor phases) were present during komatiite melting. In the Kaapvaal craton, garnet exsolution upon significant cooling occurred as early as 3.2 Ga and geobarometry of diamond inclusions from ancient kimberlites also supports cool Archaean cratonic geotherms. This requires that some mantle roots have extended to 300 to possibly 400 km and that early cratons must have been much larger than 500 km in diameter.We maintain that the Archaean-Proterozoic boundary continues to be of geological significance, despite the recognition that upper crustal chemistry, as sampled by sedimentary rocks, became more evolved from ca. 3 Ga onwards. The boundary coincides with the disappearance of widespread komatiite and marks the end of formation of typical refractory cratonic lithosphere. This may signify a fundamental change in the thermal structure of the mantle after which upwellings no longer resulted in very high temperature perturbations. One school of thought is that the thermal re-ordering occurred at the core-mantle boundary whereas others envisage Archaean plumes to have originated at the base of the upper mantle. Here we speculate that Archaean cratonic roots may contain remnants of older domains of non-convecting mantle. These domains are potential carriers of isotope anomalies and their base could have constituted a mechanical and thermal boundary layer. Above laterally extensive barriers, emerging proto-cratons were protected from the main mantle heat loss. The eventual collapse of these mechanical barriers terminated very high temperature upwellings and dismembered portions of the barrier were incorporated into the cratonic mantle during the final Neoarchaean ‘superplume’ event. The surviving cratons may therefore preserve biased evidence of geological processes that operated during the Archaean.

Geochemistry and petrogenesis of Archean mafic rocks from the Amsaga area, West African craton, Mauritania

Determining the extent of mantle mixing during the Hadean-Archean is an integral factor in our understanding of early geodynamic processes as well as the speed and degree of mantle homogenisation. If a dynamic convecting mantle was the predominant regime it would be expected that early formed isotopic anomalies would be quickly homogenised, whilst in a stagnant lid regime these anomalies might last for hundreds of millions of years. Archean terranes are dominated by felsic tonalite, trondhjemite and granodiorite rocks, as such these rocks have been the main rock type studied, even though they are not formed by primary mantle melts. Therefore, in this study, we have focused on mafic rock samples as tracers of primary mantle melting, from the relatively unknown West African craton. The mafic rocks have undergone metamorphism to granulite facies with the majority of samples retrogressed to amphibolite facies. Major element compositions reveal that the protolith was tholeiitic basalt. The majority of trace elements display limited mobility, as primary correlations with Zr are still present. Trace element patterns are typical for Archean mafic rocks, with Nb-Ta and Ti depletions. The meta-basalts yield a 147Sm-143Nd errorchron with an age of 3300 ± 300 Ma, with initial εNd of +4.4. The Nd compositions indicate that the meta-basalts have experienced minimal crustal assimilation and retain primary geochemical attributes. A positive initial εNd for the meta-basalts suggests that the magmatic protolith evolved from an already differentiated source. Nevertheless, 142Nd compositions are within error of modern day terrestrial, as such, the protolith for these samples either did not experience any early differentiation, or that mantle convection had homogenised any anomalous signal. These results highlight the lack of large (>±8 µ142Nd) 142Nd anomalies detected from outside the North Atlantic and Superior Cratons, suggesting that Archean mantle dynamics was complex, with different processes occurring on different parts of Earth, similar to today.

The Po River Water Isotopes during the Drought Condition of the Year 2017

The year 2017 was anomalously warm and dry across the whole Italian Peninsula, and the paucity of precipitation was emphasized during the extreme summer drought of the main Italian river, i.e., the Po river, which was characterized by a discharge persistently below 600 m3/s (in spite of the average discharge of 1500 m3/s). During these extreme conditions, the Po river oxygen and hydrogen stable isotopes (δD, δ18O) displayed a relation (δD = 6.1*δ18O − 6.6) significantly different from that recorded in the previous investigation of the years 2012–2014 (δD = 7.5*δ18O + 6.5). The lowering of the slope and the negative intercept clearly reflect the transition toward arid conditions that characterized the investigated period. The difference is expressed by the derivative parameter Line-Conditioned excess (LC-exc), which better describes the compositional difference of Po river water in the year 2017 with respect to that of the period 2012–2014, when the system was less affected by warm or dry conditions and the river discharge was more similar to the historical trends. The isotopic anomaly observed in 2017 throughout the river is even greater in the terminal part of the river, where in the meanders of the deltaic branches, the river flow progressively slows down, suffering significant evaporation. The isotopic signature of the water appears, therefore, an appropriate tool to monitor the watershed response to evolving environmental conditions. These sensitive isotopic parameters could be interpreted as “essential climate variables” (ECV) that are physical, chemical, or biological geo-referenced parameters that critically contribute to the characterization of Earth’s climate. Future research needs to find relationships between ECV (including the water stable isotopes) and the evolution of ecosystems, which especially in the Mediterranean area, appear to be fragile and severely affected by natural and anthropogenic processes.