Zinc isotope fractionation during mantle melting and constraints on the Zn isotope composition of Earth’s upper mantle

2017 ◽  
Vol 198 ◽  
pp. 151-167 ◽  
Author(s):  
Ze-Zhou Wang ◽  
Sheng-Ao Liu ◽  
Jingao Liu ◽  
Jian Huang ◽  
Yan Xiao ◽  
...  
Keyword(s):  
Upper Mantle ◽  
Isotope Fractionation ◽  
Isotope Composition ◽  
Mantle Melting ◽  
Zinc Isotope

Zinc isotope fractionation at destructive plate margins and potential implications for the global recycling signature

2020 ◽  
Author(s):  
Carolina Rosca ◽  
Stephan König ◽  
Marie-Laure Pons ◽  
Ronny Schoenberg
Keyword(s):  
Subduction Zones ◽  
Isotope Fractionation ◽  
Isotope Composition ◽  
Mobile Element ◽  
Mantle Melting ◽  
Fractionation Process ◽  
Zinc Isotope ◽  
Sw Pacific ◽  
The Individual ◽  
Subduction Input

<p>Our understanding regarding the behaviour of the fluid mobile element Zn at destructive plate margins is limited. In particular the fractionation mechanisms and input-output mass-balance remains to be investigated due to implications for the spatio-temporal cycling of this vital and socio-economically relevant element. In this study, we investigate the Zn isotope systematics of subduction input provided by IODP samples from the SW Pacific in comparison to lavas from the central Tonga arc, addressed as a worldwide endmember in terms of pre-subduction mantle wedge depletion. With an improved analytical precision, we report subtle, yet resolvable Zn isotope variations between the central Tongan islands, with an overall statistically relevant variation of 0.05‰ (at ±0.014‰ 2SD). The signatures are all > 0.1‰ lighter than the subduction input at this site, suggesting a fractionation process during subduction. After careful extraction of the isotopic effect caused by mantle melting processes (using DMM δ<sup>66/64</sup>Zn <sub>JMC-Lyon </sub>provided by Sossi et al. (2018) and Wang et al. (2017) and melt extraction indices such as Sm/La, Zr/Nb, and Zn/La), a pronounced negative correlation is observed between the Zn isotopic composition of the lavas and key fluid indicators such as Ba/Th and Ce/Pb. Together with predictions from <em>ab initio</em> calculations and mixing models performed between Indian DMM and Rayleigh dehydration of the subducting slab, we attribute the remaining, subtle Zn isotope variations to additions by Cl-rich fluids to the individual mantle wedges. A maximum of 5% chlorine-fluid contribution is suggested for the magmatic source of Tofua, whereas smaller proportions are estimated for Kao, Late and Ata. Overall, this study sheds new light on Zn fractionation mechanisms in sediment-poor subduction zones. Implications for the long-term Zn recycling will be addressed in this presentation.</p><p>References:</p><p>Sossi, P.A., Nebel, O., O’Neill, H.S.C., Moynier, F., 2018. Zinc isotope composition of the Earth and its behaviour during planetary accretion. Chemical Geology 447, 73-84.</p><p>Wang, Z.-Z., Liu, S.-A., Liu, J., Huang, J., Xiao, Y., Chu, Z.-Y., Zhao, X.-M., Tang, L., 2017. Zinc isotope fractionation during mantle melting and constraints on the composition of Earth’s upper mantle. Geochimica et Cosmochimica Acta 198, 151- 167.</p>

scholarly journals Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

2015 ◽  
Vol 15 (12) ◽  
pp. 6867-6877 ◽  
Author(s):  
S. J. Allin ◽  
J. C. Laube ◽  
E. Witrant ◽  
J. Kaiser ◽  
E. McKenna ◽  
...  
Keyword(s):  
Isotope Fractionation ◽  
Isotope Composition ◽  
Stratospheric Ozone ◽  
Standard Uncertainty ◽  
Gas Chromatography Mass Spectrometry ◽  
Sources And Sinks ◽  
Chlorine Isotope ◽  
Tropospheric Measurements ◽  
Single Detector

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.

scholarly journals Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

2014 ◽  
Vol 14 (23) ◽  
pp. 31813-31841
Author(s):  
S. J. Allin ◽  
J. C. Laube ◽  
E. Witrant ◽  
J. Kaiser ◽  
E. McKenna ◽  
...  
Keyword(s):  
Isotope Fractionation ◽  
Isotope Composition ◽  
Stratospheric Ozone ◽  
Isotope Ratios ◽  
Gas Chromatography Mass Spectrometry ◽  
Chlorine Isotope ◽  
Site Model ◽  
Tropospheric Measurements ◽  
Single Detector

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.

An experimental study of carbon-isotope fractionation between diet, hair, and feces of mammalian herbivores

2003 ◽  
Vol 81 (5) ◽  
pp. 871-876 ◽  
Author(s):  
Matt Sponheimer ◽  
Todd Robinson ◽  
Linda Ayliffe ◽  
Ben Passey ◽  
Beverly Roeder ◽  
...  
Keyword(s):  
Carbon Isotope ◽  
Carbon Isotopes ◽  
Isotope Fractionation ◽  
Cynodon Dactylon ◽  
Isotope Composition ◽  
Mammalian Herbivores ◽  
Carbon Isotope Fractionation ◽  
Tropical Environments ◽  
The Mean ◽  
Lama Pacos

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.

An easy-to-use, low-cost evaporation protection to collect more reliable stable water isotope data with Teledyne ISCO portable samplers

2021 ◽  
Author(s):  
Jana von Freyberg ◽  
Julia L. A. Knapp ◽  
Andrea Rücker ◽  
Bjørn Studer ◽  
Massimiliano Zappa ◽  
...  
Keyword(s):  
Water Samples ◽  
Isotope Fractionation ◽  
Field Experiments ◽  
Isotope Composition ◽  
Ambient Conditions ◽  
Storage Duration ◽  
Full Size ◽  
Isotope Data ◽  
Protection Method ◽  
Wide Range

<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>

No ion is an island: Multiple ions involved during boron incorporation into CaCO3

2021 ◽  
Author(s):  
Michael Henehan ◽  
Christa Klein-Gebbinck ◽  
Gavin Foster ◽  
Jill Wyman ◽  
Mathis Hain ◽  
...  
Keyword(s):  
Calcium Carbonate ◽  
Isotope Fractionation ◽  
Isotope Composition ◽  
Boron Isotope ◽  
Minor Role ◽  
Growth Mechanisms ◽  
Minor Elements ◽  
Vital Effects ◽  
Biogenic Carbonates ◽  
Trace And Minor Elements

<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>

scholarly journals Sabkha dolomite as an archive for the magnesium isotope composition of seawater

Geology ◽  
2020 ◽  
Author(s):  
Netta Shalev ◽  
Tomaso R.R. Bontognali ◽  
Derek Vance
Keyword(s):  
Pore Water ◽  
Formation Mechanism ◽  
Isotope Fractionation ◽  
Isotope Composition ◽  
Sole Source ◽  
Formation Temperature ◽  
Water And Sediment ◽  
Rock Record ◽  
Mg Isotopes ◽  
Dolomite Formation

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.

scholarly journals Technical note: Lithium isotopes in dolostone as a palaeo-environmental proxy – an experimental approach

2019 ◽  
Vol 15 (2) ◽  
pp. 635-646 ◽  
Author(s):  
Holly L. Taylor ◽  
Isaac J. Kell Duivestein ◽  
Juraj Farkas ◽  
Martin Dietzel ◽  
Anthony Dosseto
Keyword(s):  
Isotope Fractionation ◽  
Isotope Composition ◽  
Relative Proportion ◽  
Significant Proportion ◽  
Technical Note ◽  
Fractionation Factor ◽  
Calcium Carbonates ◽  
Marine Carbonates ◽  
Li Isotope ◽  
Environmental Proxy

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.

scholarly journals Pervasive upper mantle melting beneath the western US

2017 ◽  
Vol 463 ◽  
pp. 25-35 ◽  
Author(s):  
Saswata Hier-Majumder ◽  
Benoit Tauzin
Keyword(s):  
Upper Mantle ◽  
Mantle Melting ◽  
Western Us

scholarly journals Zinc isotope fractionation during grain filling of wheat and a comparison of zinc and cadmium isotope ratios in identical soil-plant systems

2018 ◽  
Vol 219 (1) ◽  
pp. 195-205 ◽  
Author(s):  
Matthias Wiggenhauser ◽  
Moritz Bigalke ◽  
Martin Imseng ◽  
Armin Keller ◽  
Corey Archer ◽  
...  
Keyword(s):  
Isotope Fractionation ◽  
Grain Filling ◽  
Isotope Ratios ◽  
Zinc Isotope
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