This study presents a methodological advancement in the field of clumped‐isotope (∆47) thermometry, specifically tailored for application to freshwater ostracods. The novel ostracod clumped isotope ...approach enables quantitative temperature and hydrological reconstruction in lacustrine records. The relationship between ∆47 and the temperature at which ostracod shell mineralized is determined by measuring ∆47 on different species grown under controlled temperatures, ranging from 4 ± 0.8 to 23 ± 0.5ºC. The excellent agreement between the presented ∆47 ostracod data and the monitored temperatures confirms that ∆47 can be applied to ostracod shells and that a vital effect is absent outside the uncertainty of measurements. Results are consistent with the carbonate clumped‐isotope unified calibration (Anderson et al., 2021, https://doi.org/10.1029/2020gl092069), therefore, an ostracod‐specific calibration is not needed. The ostracod clumped‐isotope thermometer represents a powerful tool for terrestrial paleoclimate studies all around the world, as lakes and ostracods are found in all climatic belts.
Plain Language Summary
In the framework of global warming, the reconstruction of past climatic conditions is important to understand the future evolution of climate and its impact. Lake sediments can be used as archives to quantify these effects. This study presents a novel paleo‐thermometer based on the application of clumped‐isotope technique (i.e., measurement of the number of 13C–18O bonds in carbonate minerals that depends on the temperature of carbonate precipitation) on carbonatic microcrustacea, named ostracods that commonly live in lakes. By using ostracods that formed their shells at known temperatures, we demonstrate that they can be easily used to reconstruct water temperature and hydrological conditions (precipitation/evaporation). The ostracod clumped‐isotope thermometer represents a powerful tool for terrestrial paleoclimate studies around the world, as lakes and ostracods are located in all climatic belts.
Key Points
∆47—ostracod signal accurately records the shell calcification temperature
∆47—ostracod signal is not affected by the so called “vital effect”
The unified calibration of Anderson et al. (2021) can be used to convert the ∆47—ostracod signal into accurate temperatures
Northwest Africa (NWA) 7034 and paired stones represent unique samples of martian polymict regolith breccia. Multiple breccia subsamples characterized in this work confirm highly siderophile element ...(HSE: Re, Os, Ir, Ru, Pt, Pd) contents that are consistently elevated (e.g., Os ∼9.3–18.4ppb) above indigenous martian igneous rocks (mostly <5ppb Os), equivalent to ∼3wt% of admixed CI-type carbonaceous chondritic material, and occur in broadly chondrite-relative proportions. However, a protracted history of impactor component (metal and sulfide) breakdown and redistribution of the associated HSE has masked the original nature of the admixed meteorite signatures. The present-day 187Os/188Os ratios of 0.119–0.136 record a wider variation than observed for all major chondrite types. Combined with the measured 187Re/188Os ratios of 0.154–0.994, the range in Os isotope ratios indicates redistribution of Re and Os from originally chondritic components early in the history of the regolith commencing at ∼4.4Ga. Superimposed recent Re mobility reflects exposure and weathering at or near the martian and terrestrial surfaces. Elevated Os concentrations (38.0 and 92.6ppb Os), superchondritic Os/HSE ratios, and 187Os/188Os of 0.1171 and 0.1197 measured for two subsamples of the breccia suggest the redistribution of impactor material at ∼1.5–1.9Ga, possibly overlapping with a (partial) resetting event at ∼1.4Ga recorded by U–Pb isotope systematics in the breccia. Martian alteration of the originally chondritic HSE host phases, to form Os-Ir-rich nuggets and Ni-rich pyrite, implies the influence of potentially impact-driven hydrothermal systems. Multiple generations of impactor component admixture, redistribution, and alteration mark the formation and evolution of the martian regolith clasts and matrix of NWA 7034 and paired meteorites, from the pre-Noachian until impact ejection to Earth.
The ∼1.88km diameter Lonar impact crater formed ∼570ka ago and is an almost circular depression hosted entirely in the Poladpur suite of the ∼65Ma old basalts of the Deccan Traps. To understand the ...effects of impact cratering on basaltic targets, commonly found on the surfaces of inner Solar System planetary bodies, major and trace element concentrations as well as Nd and Sr isotopic compositions were determined on a suite of selected samples composed of: basalts, a red bole sample, which is a product of basalt alteration, impact breccia, and impact glasses, either in the form of spherules (<1mm in diameter) or non-spherical impact glasses (>1mm and <1cm). These data include the first highly siderophile element (HSE) concentrations for the Lonar spherules. The chemical index of alteration (CIA) values for the basalts and impact breccia (36.4–42.7) are low while the red bole sample shows a high CIA value (55.6 in the acid-leached sample), consistent with its origin by aqueous alteration of the basalts. The Lonar spherules are classified into two main groups based on their CIA values. Most spherules show low CIA values (Group 1: 34.7–40.5) overlapping with the basalts and impact breccia, while seven spherules show significantly higher CIA values (Group 2: >43.0). The Group 1 spherules are further subdivided into Groups 1a and 1b, with Group 1a spherules showing higher Ni and mostly higher Cr compared to the Group 1b spherules. Iridium and Cr concentrations of the spherules are consistent with the admixture of 1–8wt% of a chondritic impactor to the basaltic target rocks. The impactor contribution is most prominent in the Group 1a and Group 2 spherules, which show higher Ni/Co, Ni/Cr and Cr/Co ratios compared to the target basalts. In contrast, the Group 1b spherules show major and trace element compositions that overlap with those of the impact breccia and are characterized by high EFTh (Enrichment Factor for Th defined as the Nb-normalized concentration of Th relative to that of the average basalt) as well as fractionated La/Sm(N), and higher large ion lithophile element (LILE) concentrations compared to the basalts. The relatively more radiogenic Sr and less radiogenic Nd isotopic composition of the impact breccia and non-spherical impact glasses compared to the target basalts are consistent with melting and mixing of the Precambrian basement beneath the Deccan basalt with up to 15wt% contribution of the basement to these samples. Variations in the moderately siderophile element (MSE) concentration ratios of the impact breccia as well as all the spherules are best explained by contributions from three components – a chondritic impactor, the basaltic target rocks at Lonar and the basement underlying the Deccan basalts. The large variations in concentrations of volatile elements like Zn and Cu and correlated variations of EFCu-EFZn, EFPb-EFZn, EFK-EFZn and EFNa-EFZn, particularly in the Group 1a spherules, are best explained by evaporation-condensation effects during impact. While most spherules, irrespective of their general major and trace element composition, show a loss in volatile elements (e.g., Zn and Cu) relative to the target basalts, some spherules, mainly of Group 1, display enrichments in these elements that are interpreted to reflect the unique preservation of volatile-rich vapour condensates resulting from geochemical fractionation in a vertical direction within the vapour cloud.
•C, Sr, Nd and trace element chemostratigraphy of Neoproterozoic Witvlei Group carbonates.•Zircon provenance of Witvlei Basin sandstones is comparable with nearby Ghanzi Group tracing erosion of the ...Kalahari Craton.•Variable weathering fluxes and ocean circulation patterns affecting post-glacial seawater.•Putative Shuram anomaly equivalent coincides with a decrease in bio-essential trace metals and less oxidised surface waters.•Bio-essential and redox-sensitive trace element enrichments in late Ediacaran seawater similar to the Phanerozoic.
The Neoproterozoic witnessed several low latitude glaciations (i.e., the Sturtian, Marinoan and Gaskiers glaciations) and the geodynamic reorganization of cratonic blocks after the breakup of Rodinia. Trace element and stable isotope geochemistry from approximately coeval carbonate deposits on continental marginal sea and foreland basins (Yangtze Platform, China; Otavi and Nama Groups, Namibia) have shown fluctuating oxygen increase on the marine shelves. To gain an increasingly global picture of the bio-geochemical conditions in late Neoproterozoic seawater, we here present new redox-sensitive trace element, stable (C, O) and radiogenic (Nd, Sr) isotope records of carbonates from the Cryogenian Blaubeker and Court, and the Ediacaran Buschmannsklippe Formations (Witvlei Group, Namibia). Shale-normalised REE + Y patterns of post-Sturtian and post-Marinoan carbonates parallel modern seawater showing positive La, Gd and Y anomalies. Negative Ce anomalies argue for their preservation in increasingly more oxidising sea/porewater conditions in the Witvlei Basin from the Ediacaran on. While Cryogenian carbonates underwent radiogenic basin-fluid type overprinting, Ediacaran carbonates upsection record pristine Sr isotopic compositions that match the global Neoproterozoic seawater curve. Partly coupled negative correlations between Sr and Nd suggest long-term shifts in continental weathering and short-term changes in ocean circulation patterns. The δ13Ccarb values range from −7.2 to +3.5 ‰ and record a negative isotope excursion in the upper part of the Witvlei stratigraphy. This excursion might be equivalent to the ‘Shuram’ carbon isotope excursion (CIE). However, the causes, global extent and correlation of the Shuram CIE are still debated. Typical for carbonates of the putative Shuram excursion are less pronounced Ce anomalies, lower Y/Ho ratios, and lower bio-essential and redox-sensitive trace metal concentrations, arguing for periodic redoxcline oscillations in a redox-stratified late Neoproterozoic shelf environment. The overall long-term decrease in redox-sensitive element enrichments throughout the Witvlei Group argues for a progressively increasing, presumably biologically-driven metal cycling towards values typical for Phanerozoic carbonates. The combination of changes in local weathering flux and ambient redox conditions in the late Neoproterozoic ocean may have caused dynamic (bio)geochemical metal cycling, predating (and possibly promoting) the metazoan radiation documented in the overlying Nama Group.
The end-Triassic extinction event (∼ 201.5 Ma) is one of the five major mass extinction events in Earth's history, however, considerable discussion continues on the exact causes and timing of the ...event. This is because, whilst certain geochemical data on T-J sections appears to be largely comparable globally, with for example a significant (up to 6‰) negative carbon-isotope (δ13C) excursion at the extinction horizon, more often than not other geochemical variations are neither uniform nor fully consistent between sections. Critical to this discussion is that the majority of the studied sections containing the end-Triassic extinction event are limited to shallow marine or terrestrial sections, which are prone to discontinuities and hiatuses. In this study, we present carbon isotopes (δ13Ccarb), total organic carbon (TOC), major and trace, mercury (Hg) and highly siderophile elements (HSE), osmium-isotope compositions and paleomagnetic data of a relatively less studied deep-marine T-J succession in the Budva Basin, Čanj, Montenegro. At Čanj, deep-marine Triassic limestones are abruptly interrupted by a ∼ 6 cm finely laminated clay layer, before transitioning to more argillaceous Jurassic red beds. The clay layer is interpreted to represent the end-Triassic extinction interval and is characterized by a negative carbon isotope excursion, relative heavy rare earth element (HREE) enrichment, Hg increase, HSE enrichment and a sharp shift to unradiogenic osmium-isotopic ratios. This establishes the Čanj section as a unique and well-preserved outcrop that exquisitely encapsulates the end-Triassic extinction in the Tethyan marine realm. The distinct geochemical markers recorded at Čanj are consistent with the Central Atlantic Magmatic Province as the main driver behind the end-Triassic extinction.
•In-depth geochemical study of a little known deep-marine T-J succession in Čanj, Montenegro.•Section encapsulates the end-Triassic extinction interval in the Tethyan deep sea.•Triassic limestones are abruptly interrupted by a thin ∼6 cm clay layer.•Overlying Jurassic red beds are distinctly different from the limestones.•Geochemical markers at Čanj consistent with the Central Atlantic Magmatic Province.
Geochemical proxy records from calcite shells of bivalves constitute an important archive for the reconstruction of palaeoenvironmental conditions on sub-annual timescales. However, the incorporation ...of these trace element and stable isotope proxies into the shell is influenced by a multitude of physiological and environmental factors that need to be disentangled to enable reliable reconstruction of palaeoclimate and palaeoenvironment. In this study, records of multiple proxies in three bivalve taxa from the same late Campanian locality in Oman are used to study the expression of various geochemical proxies in relation to each other and to the palaeoenvironment. Micro-X-Ray Fluorescence mapping allows the localization, discussion and evasion of diagenetically altered parts of the fossil shells. X-Ray Fluorescence line scanning calibrated with Laser Ablation Inductively Coupled Plasma Mass Spectrometry is used to measure trace element profiles through well-preserved calcitic parts of the shells. Records of stable carbon and oxygen isotope ratios of shell calcite are combined with these high-resolution trace element concentration profiles to study sub-annual variations in shell chemistry and reconstruct changes in the palaeoenvironment of the bivalves on a seasonal scale. Spectral analysis routines are used to detect cyclicity in stable isotope (δ18O and δ13C) and trace element (Mg/Ca, Sr/Ca, S/Ca and Zn/Ca) records. Differences in seasonal expression between these chemical proxies and between individual shells are discussed in terms of the relative influence of palaeoenvironment and potential species-specific physiological effects. Stable oxygen isotope ratios between shells suggest a local palaeotemperature seasonality of 8°C around an annual mean of 28°C, with the shell of the rudistid Torreites sanchezi milovanovici yielding slightly higher average temperatures. The discussion of the application of various Mg/Ca palaeotemperature calibrations on Mg/Ca records in these bivalve species emphasizes the complexity of using trace element proxies in extinct bivalve species. It shows that long-term changes in Mg/Ca ratios in ocean water need to be taken into account and that Mg/Ca ratios in bivalves might be influenced by vital effects. Sr/Ca and S/Ca ratios in these fossil taxa are likely controlled by growth and metabolic rates of the shell, although an influence of local salinity on strontium-to-calcium ratios cannot be excluded. Sub-annual variations in zinc concentrations in shell calcite may reflect seasonal variations in palaeoproductivity and redox conditions in the water column.
•Trace element and stable isotope profiles measured in three late Campanian bivalves.•Proxy records are used to reconstruct palaeoseasonality and palaeoenvironment.•δ18O yields 8°C seasonality around mean of 28°C, Mg/Ca-temperatures were unreliable.•Zn/Ca records indicate seasonal changes in redox conditions and palaeoproductivity.•Sr/Ca and S/Ca trace seasonal fluctuations in shell growth and metabolic rate.
The high temperatures reached during cremation lead to the destruction of organic matter preventing the use of traditional isotopic methods for dietary reconstructions. Still, strontium isotope (
Sr/
...Sr) and concentration (Sr) analyses of cremated human remains offer a novel way to assess changing consumption patterns in past populations that practiced cremation, as evidenced by a large amount of new data obtained from Metal Ages and Gallo-Roman human remains from Destelbergen, Belgium. The Gallo-Roman results show significantly higher Sr and a narrower interquartile range in
Sr/
Sr (0.7093-0.7095), close to the value of modern-day seawater (0.7092). This contrasts with the Metal Ages results, which display lower concentrations and a wider range in
Sr/
Sr (0.7094-0.7098). This typical Sr signature is also reflected in other sites and is most likely related to an introduction of marine Sr in the form of salt as a food preservative (e.g. salt-rich preserved meat, fish and fish sauce). Paradoxically, this study highlights caution is needed when using
Sr/
Sr for palaeomobility studies in populations with high salt consumption.
Various iron and stony-iron meteorites have been characterized for their Ni and Fe isotopic compositions using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) after sample ...digestion and chromatographic separation of the target elements in an attempt to further constrain the planetary differentiation processes that shifted these isotope ratios and to shed light on the formational history and evolution of selected achondrite parent body asteroids. Emphasis was placed on spatially resolved isotopic analysis of iron meteorites, known to be inhomogeneous at the μm to mm scale, and on the isotopic characterization of adjacent metal and silicate phases in main group pallasites (PMG), mesosiderites, and the IIE and IAB complex silicate-bearing iron meteorites. In a 3-isotope plot of 60/58Ni versus62/58Ni, the slope of the best-fitting straight line through the laterally resolved Ni isotope ratio data for iron meteorites reveals kinetically controlled isotope fractionation (βexper=1.981±0.039, 1 SD), predominantly resulting from sub-solidus diffusion (with the fractionation exponent β connecting the isotope fractionation factors, as α62/58=α60/58β). The observed relation between δ56/54Fe and Ir concentration in the metal fractions of PMGs and in IIIAB iron meteorites indicates a dependence of the bulk Fe isotopic composition on the fractional crystallization of an asteroidal metal core. No such fractional crystallization trends were found for the corresponding Ni isotope ratios or for other iron meteorite groups, such as the IIABs. In the case of the IIE and IAB silicate-bearing iron meteorites, the Fe and Ni isotopic signatures potentially reflect the influence of impact processes, as the degree of diffusion-controlled Ni isotope fractionation is closer to that of Fe compared to what is observed for magmatic iron meteorite types. Between the metal and olivine counterparts of pallasites, the Fe and Ni isotopic compositions show clearly resolvable differences, similar in magnitude but opposite in sign (Δ56/54Femet-oliv of +0.178±0.092‰ and Δ60/58Nimet-oliv of −0.212±0.082‰, 2SD). As such, the heavier Fe isotope ratios for the metal (δ56/54Fe=+0.023‰ to +0.247‰) and lighter values for the corresponding olivines (δ56/54Fe=−0.155‰ to −0.075‰) are interpreted to reflect later-stage Fe isotopic re-equilibration between these phases, rather than a pristine record of mantle-core differentiation. In the case of mesosiderites, the similarly lighter Ni and Fe isotopic signatures found for the silicate phase (−0.149‰ to +0.023‰ for δ60/58Ni, −0.214‰ to −0.149‰ for δ56/54Fe) compared to the metal phase (+0.168‰ to +0.191‰ for δ60/58Ni, +0.018‰ to +0.120‰ for δ56/54Fe) likely result from Fe and Ni diffusion. Overall, the Fe and Ni isotopic compositions of iron-rich meteorites reflect multiple, often superimposed, processes of equilibrium or kinetic nature, illustrating convoluted parent body histories and late-stage interaction between early-formed planetesimal reservoirs.
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