Tin isotope fractionation during magmatic processes and the isotope composition of the bulk silicate Earth

2018 ◽  
Vol 228 ◽  
pp. 320-335 ◽  
Author(s):  
Xueying Wang ◽  
Quentin Amet ◽  
Caroline Fitoussi ◽  
Bernard Bourdon
2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Sune G. Nielsen ◽  
David V. Bekaert ◽  
Maureen Auro

AbstractIsotopic measurements of lunar and terrestrial rocks have revealed that, unlike any other body in the solar system, the Moon is indistinguishable from the Earth for nearly every isotopic system. This observation, however, contradicts predictions by the standard model for the origin of the Moon, the canonical giant impact. Here we show that the vanadium isotopic composition of the Moon is offset from that of the bulk silicate Earth by 0.18 ± 0.04 parts per thousand towards the chondritic value. This offset most likely results from isotope fractionation on proto-Earth during the main stage of terrestrial core formation (pre-giant impact), followed by a canonical giant impact where ~80% of the Moon originates from the impactor of chondritic composition. Our data refute the possibility of post-giant impact equilibration between the Earth and Moon, and implies that the impactor and proto-Earth mainly accreted from a common isotopic reservoir in the inner solar system.


2015 ◽  
Vol 15 (12) ◽  
pp. 6867-6877 ◽  
Author(s):  
S. J. Allin ◽  
J. C. Laube ◽  
E. Witrant ◽  
J. Kaiser ◽  
E. McKenna ◽  
...  

Abstract. The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.


2014 ◽  
Vol 14 (23) ◽  
pp. 31813-31841
Author(s):  
S. J. Allin ◽  
J. C. Laube ◽  
E. Witrant ◽  
J. Kaiser ◽  
E. McKenna ◽  
...  

Abstract. The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are (−2.4 ± 0.5) and (−2.3 ± 0.4)‰ for CFC-11, (−12.2 ± 1.6) and (−6.8 ± 0.8)‰ for CFC-12 and (−3.5 ± 1.5) and (−3.3 ± 1.2)‰ for CFC-113, respectively. Assuming a constant source isotope composition, we estimate the expected trends in the tropospheric isotope signature of these gases due to their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these model results to the long-term δ(37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (NEEM site) and Antarctica (Fletcher Promontory site). Model trends agree with tropospheric measurements within analytical uncertainties. From 1970 to the present-day, we find no evidence for variations in chlorine isotope ratios associated with changes in CFC manufacturing processes. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes, using a single-detector gas chromatography-mass spectrometry system.


2003 ◽  
Vol 81 (5) ◽  
pp. 871-876 ◽  
Author(s):  
Matt Sponheimer ◽  
Todd Robinson ◽  
Linda Ayliffe ◽  
Ben Passey ◽  
Beverly Roeder ◽  
...  

The carbon-isotope composition of hair and feces offers a glimpse into the diets of mammalian herbivores. It is particularly useful for determining the relative consumption of browse and graze in tropical environments, as these foods have strongly divergent carbon-isotope compositions. Fecal δ13C values reflect the last few days consumption, whereas hair provides longer term dietary information. Previous studies have shown, however, that some fractionation occurs between dietary δ13C values and those of hair and feces. Accurate dietary reconstruction requires an understanding of these fractionations, but few controlled-feeding studies have been undertaken to investigate these fractionations in any mammalian taxa, fewer still in large mammalian herbivores. Here, we present data from the first study of carbon-isotope fractionation between diet, hair, and feces in multiple herbivore taxa. All taxa were fed pure alfalfa (Medicago sativa) diets for a minimum period of 6 months, at which point recently grown hair was shaved and analyzed for carbon isotopes. The mean observed diet–hair fractionation was +3.2‰, with a range of +2.7 to +3.5‰. We also examined diet–feces fractionation for herbivores on alfalfa and bermudagrass (Cynodon dactylon) feeds. The mean diet–feces fractionation for both diets was –0.8‰, with less fractionation for alfalfa (–0.6‰) than bermudagrass (–1.0‰). Fecal carbon turnover also varies greatly between taxa. When diets were switched, horse (Equus caballus) feces reflected the new diet within 60 h, but alpaca (Lama pacos) feces did not equilibrate with the new diet for nearly 200 h. Thus, fecal carbon isotopes provide far greater dietary resolution for hindgut-fermenting horses than foregut-fermenting alpacas.


2021 ◽  
Author(s):  
Jana von Freyberg ◽  
Julia L. A. Knapp ◽  
Andrea Rücker ◽  
Bjørn Studer ◽  
Massimiliano Zappa ◽  
...  

<p>Off-the-shelf portable automatic water samplers, such as the 6712 full-size portable sampler (Teledyne ISCO, Lincoln, USA), are often used in remote locations to collect precipitation or streamwater for subsequent analysis of deuterium and oxygen-18.  The bottles inside these automatic samplers remain open during the full duration of sampler deployment and the collected water samples can thus be subjected to evaporation and vapor exchange.  Both processes are known to alter the isotope composition of the water sample, and thus the questions arise as to 1) how credible the isotope measurements from automatically collected water samples are and 2) how can these isotope effects in the automatic water sampler be reduced?</p><p>We evaluated these questions through laboratory and field experiments in which we quantified the change in isotope composition in the water samples with respect to ambient conditions (air temperature and relative humidity), storage duration, and sample volume.  We found that isotope fractionation in the water samples was substantial under very warm and dry condition, when sample volumes are small or when sample storage exceeded 10 days.  To address these problems, we have designed an evaporation protection method which modifies autosampler bottles using a syringe housing and silicone tube.  We performed paired experiments with open vs. evaporation-protected bottles in Teledyne ISCO 6712 full-size portable samplers to evaluate our design.  We could show that the evaporation protection successfully reduced isotope fractionation in the water samples for storage durations of up to 24 days and for a wide range of ambient conditions; e.g., while deuterium concentrations in the water samples in open bottles changed by ca. 3‰ under very warm and dry conditions, no isotope effect was measured in the bottles equipped with the evaporation protection. Because our design is very cost efficient it can easily be implemented to upgrade Teledyne ISCO’s 6712 full-size portable samplers or other similar devices for collecting more reliable isotope data.</p>


2021 ◽  
Author(s):  
Michael Henehan ◽  
Christa Klein-Gebbinck ◽  
Gavin Foster ◽  
Jill Wyman ◽  
Mathis Hain ◽  
...  

<p>Boron isotope ratios, as measured in marine calcium carbonate, are a proven tracer of past seawater and calcifying fluid pH and thus a powerful tool for the reconstruction of past atmospheric CO<sub>2</sub> and monitoring of coral physiology. For such applications, understanding the inorganic baseline upon which foraminiferal vital effects or coral pH upregulation are superimposed should be an important prerequisite. Yet, investigations into boron isotope fractionation in synthetic CaCO<sub>3 </sub>polymorphs have often reported variable and even conflicting results, implying that we may not fully understand pathways of boron incorporation into calcium carbonate.  Here we address this topic with experimental data from calcite and aragonite precipitated across a range of pH in the presence of both Mg and Ca. We confirm the results of previous studies that the boron isotope composition of inorganic aragonite precipitates closely reflects that of aqueous borate ion, but that calcites display a higher degree of scatter, and diverge from the boron isotope composition of borate ion at low pH. We discuss these findings with reference to the simultaneous incorporation of other trace and minor elements, and highlight a number of mechanisms by which crystal growth mechanisms may influence the concentration and isotope composition of boron in CaCO<sub>3</sub>. In particular, we highlight the potential importance of surface electrostatics in driving variability in published synthetic carbonate datasets. Importantly for palaeo-reconstruction, however, these electrostatic effects are likely to play a much more minor role during natural precipitation of biogenic carbonates.</p>


Geology ◽  
2020 ◽  
Author(s):  
Netta Shalev ◽  
Tomaso R.R. Bontognali ◽  
Derek Vance

Recent studies have uncovered the potential of Mg isotopes (δ26Mg) for studying past ocean chemistry, but records of such data are still scarce. Dolomite has been suggested as a promising archive for δ26Mg of seawater. However, its enigmatic formation mechanism and the difficulty in precipitating dolomite in the laboratory at surface temperatures decrease confidence in the interpretation of δ26Mg values from the rock record. To evaluate factors determining the δ26Mg of dolomite, we studied pore water and sediment from Dohat Faishakh Sabkha, Qatar—one of the rare environments where dolomite is currently forming. The δ26Mg values of the dolomite (–2.56‰ to –1.46‰) are lower than that of seawater (–0.83‰), whereas δ26Mg values of pore water (–0.71‰ to –0.14‰) are higher. The isotope fractionation accompanying dolomite formation is generally in accordance with an empirical fractionation from the literature, extrapolated to the sabkha’s temperature (–1.84‰ to –1.51‰). The results suggest that evaporated seawater is the sole source of Mg, and isotopically light dolomite is the major sink, so that the δ26Mg of the dolomite-forming pore water is equal to or greater than that of seawater. Thus, provided that the lowest δ26Mg value among several dolomite samples is used, and the formation temperature is known, similar sabkha-type dolomites can be utilized as an archive for δ26Mg values of ancient seawater.


2019 ◽  
Vol 15 (2) ◽  
pp. 635-646 ◽  
Author(s):  
Holly L. Taylor ◽  
Isaac J. Kell Duivestein ◽  
Juraj Farkas ◽  
Martin Dietzel ◽  
Anthony Dosseto

Abstract. Lithium (Li) isotopes in marine carbonates have considerable potential as a proxy to constrain past changes in silicate weathering fluxes and improve our understanding of Earth's climate. To date the majority of Li isotope studies on marine carbonates have focussed on calcium carbonates. The determination of the Li isotope fractionation between dolomite and a dolomitizing fluid would allow us to extend investigations to deep times (i.e. Precambrian) when dolostones were the most abundant marine carbonate archives. Dolostones often contain a significant proportion of detrital silicate material, which dominates the Li budget; thus, pretreatment needs to be designed so that only the isotope composition of the carbonate-associated Li is measured. This study aims to serve two main goals: (1) to determine the Li isotope fractionation between Ca–Mg carbonates and solution, and (2) to develop a method for leaching the carbonate-associated Li out of dolostone while not affecting the Li contained within the detrital portion of the rock. We synthesized Ca–Mg carbonates at high temperatures (150 to 220 ∘C) and measured the Li isotope composition (δ7Li) of the precipitated solids and their respective reactive solutions. The relationship of the Li isotope fractionation factor with temperature was obtained: 103ln⁡αprec-sol=-(2.56±0.27)106(1)/T2+(5.8±1.3) Competitive nucleation and growth between dolomite and magnesite were observed during the experiments; however, there was no notable effect of their relative proportion on the apparent Li isotope fractionation. We found that Li isotope fractionation between the precipitated solid and solution is higher for Ca–Mg carbonates than for Ca carbonates. If the temperature of a precipitating solution is known or can be estimated independently, the above equation could be used in conjunction with the Li isotope composition of dolostones to derive the composition of the solution and hence make inferences about the past Li cycle. In addition, we also conducted leaching experiments on a Neoproterozoic dolostone and a Holocene coral. Results show that leaching with 0.05 M hydrochloric acid (HCl) or 0.5 % acetic acid (HAc) at room temperature for 60 min releases Li from the carbonate fraction without a significant contribution of Li from the siliciclastic detrital component. These experimental and analytical developments provide a basis for the use of Li isotopes in dolostones as a palaeo-environmental proxy, which will contribute to further advance our understanding of the evolution of Earth's surface environments.


2014 ◽  
Vol 11 (24) ◽  
pp. 7207-7217 ◽  
Author(s):  
C. L. Blättler ◽  
S. M. Stanley ◽  
G. M. Henderson ◽  
H. C. Jenkyns

Abstract. Geochemical records of biogenic carbonates provide some of the most valuable records of the geological past, but are often difficult to interpret without a mechanistic understanding of growth processes. In this experimental study, Halimeda algae are used as a test organism to untangle some of the specific factors that influence their skeletal composition, in particular their Ca-isotope composition. Algae were stimulated to precipitate both calcite and aragonite by growth in artificial Cretaceous seawater, resulting in experimental samples with somewhat malformed skeletons. The Ca-isotope fractionation of the algal calcite (−0.6‰) appears to be much smaller than that for the algal aragonite (−1.4‰), similar to the behaviour observed in inorganic precipitates. However, the carbonate from Halimeda has higher Ca-isotope ratios than inorganic forms by approximately 0.25‰, likely because of Rayleigh distillation within the algal intercellular space. In identifying specific vital effects and the magnitude of their influence on Ca-isotope ratios, this study suggests that mineralogy has a first-order control on the marine Ca-isotope cycle.


2019 ◽  
Vol 259 ◽  
pp. 288-301 ◽  
Author(s):  
Yu-Han Qi ◽  
Fei Wu ◽  
Dmitri A. Ionov ◽  
Igor S. Puchtel ◽  
Richard W. Carlson ◽  
...  

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