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 Modern and Cenozoic records of magnesium behaviour from foraminiferal Mg isotopes

2014 ◽  
Vol 11 (5) ◽  
pp. 7451-7484 ◽  
Author(s):  
P. A. E. Pogge von Strandmann ◽  
J. Forshaw ◽  
D. N. Schmidt
Keyword(s):  
Isotope Composition ◽  
Single Species ◽  
Isotope Ratios ◽  
Pore Waters ◽  
The Past ◽  
Oxygen Isotope Ratios ◽  
Atmosphere System ◽  
Mg Isotopes ◽  
Dolomite Formation ◽  
Foraminiferal Record

Abstract. Magnesium is an element critically involved in the carbon cycle, because weathering of Ca–Mg silicates removes atmospheric CO2 into rivers, and formation of Ca–Mg carbonates in the oceans removes carbon from the ocean–atmosphere system. Hence the Mg cycle holds the potential to provide valuable insights into Cenozoic climate-system history, and the shift during this time from a greenhouse to icehouse state. We present Mg isotope ratios for the past 40 Myr using planktic foraminifers as an archive. Modern foraminifera, which discriminate against elemental and isotopically heavy Mg during calcification, show no correlation between the Mg isotope composition (δ26Mg) and temperature, Mg / Ca or other parameters such as carbonate saturation (Δ CO3). However, inter-species isotopic differences imply that only well-calibrated single species should be used for reconstruction of past seawater. Seawater δ26Mg inferred from the foraminiferal record decreased from ~ 0‰ at 15 Ma, to −0.83‰ at the present day, which coincides with increases in seawater lithium and oxygen isotope ratios. It strongly suggests that neither Mg concentrations nor isotope ratios are at steady-state in modern oceans, given its ~ 10 Myr residence time. From these data, we have developed a dynamic box model to understand and constrain changes in Mg sources to the oceans (rivers) and Mg sinks (dolomitisation and hydrothermal alteration). Our estimates of seawater Mg concentrations through time are similar to those independently determined by pore waters and fluid inclusions. Modelling suggests that dolomite formation and the riverine Mg flux are the primary controls on the δ26Mg of seawater, while hydrothermal Mg removal and the δ26Mg of rivers are more minor controls. Using riverine flux and isotope ratios inferred from the 87Sr / 86Sr record, the modelled Mg removal by dolomite formation shows minima in the Oligocene and at the present day (with decreasing trends from 15 Ma), both coinciding with rapid decreases in global temperatures.

scholarly journals Modern and Cenozoic records of seawater magnesium from foraminiferal Mg isotopes

2014 ◽  
Vol 11 (18) ◽  
pp. 5155-5168 ◽  
Author(s):  
P. A. E. Pogge von Strandmann ◽  
J. Forshaw ◽  
D. N. Schmidt
Keyword(s):  
Isotope Composition ◽  
Single Species ◽  
Isotope Ratios ◽  
Pore Waters ◽  
The Past ◽  
Oxygen Isotope Ratios ◽  
Atmosphere System ◽  
Mg Isotopes ◽  
Dolomite Formation ◽  
Foraminiferal Record

Abstract. Magnesium is an element critically involved in the carbon cycle, because weathering of Ca-Mg silicates removes atmospheric CO2 into rivers, and formation of Ca-Mg carbonates in the oceans removes carbon from the ocean-atmosphere system. Hence the Mg cycle holds the potential to provide valuable insights into Cenozoic climate-system history, and the shift during this time from a greenhouse to icehouse state. We present Mg isotope ratios for the past 40 Myr using planktic foraminifers as an archive. Modern foraminifera, which discriminate against elemental and isotopically heavy Mg during calcification, show no correlation between the Mg isotope composition (δ26Mg, relative to DSM-3) and temperature, Mg / Ca or other parameters such as carbonate saturation (ΔCO3). However, inter-species isotopic differences imply that only well-calibrated single species should be used for reconstruction of past seawater. Seawater δ26Mg inferred from the foraminiferal record decreased from ~0‰ at 15 Ma, to −0.83‰ at the present day, which coincides with increases in seawater lithium and oxygen isotope ratios. It strongly suggests that neither Mg concentrations nor isotope ratios are at steady state in modern oceans, given its ~10 Myr residence time. From these data, we have developed a dynamic box model to understand and constrain changes in Mg sources to the oceans (rivers) and Mg sinks (dolomitisation and hydrothermal alteration). Our estimates of seawater Mg concentrations through time are similar to those independently determined by pore waters and fluid inclusions. Modelling suggests that dolomite formation and the riverine Mg flux are the primary controls on the δ26Mg of seawater, while hydrothermal Mg removal and the δ26Mg of rivers are more minor controls. Using Mg riverine flux and isotope ratios inferred from the 87Sr / 86Sr record, the modelled Mg removal by dolomite formation shows minima in the Oligocene and at the present day (with decreasing trends from 15 Ma), both coinciding with rapid decreases in global temperatures.

scholarly journals Carbon Isotope Fractionation during the Formation of CO2 Hydrate and Equilibrium Pressures of 12CO2 and 13CO2 Hydrates

Molecules ◽  
2021 ◽  
Vol 26 (14) ◽  
pp. 4215
Author(s):  
Hiromi Kimura ◽  
Go Fuseya ◽  
Satoshi Takeya ◽  
Akihiro Hachikubo
Keyword(s):  
Carbon Isotope ◽  
Isotope Fractionation ◽  
Small Difference ◽  
Hydrate Formation ◽  
Formation Temperature ◽  
Carbon Isotope Fractionation ◽  
Unit Cell Size ◽  
Naturally Occurring ◽  
Three Phase ◽  
The Difference

Knowledge of carbon isotope fractionation is needed in order to discuss the formation and dissociation of naturally occurring CO2 hydrates. We investigated carbon isotope fractionation during CO2 hydrate formation and measured the three-phase equilibria of 12CO2–H2O and 13CO2–H2O systems. From a crystal structure viewpoint, the difference in the Raman spectra of hydrate-bound 12CO2 and 13CO2 was revealed, although their unit cell size was similar. The δ13C of hydrate-bound CO2 was lower than that of the residual CO2 (1.0–1.5‰) in a formation temperature ranging between 226 K and 278 K. The results show that the small difference between equilibrium pressures of ~0.01 MPa in 12CO2 and 13CO2 hydrates causes carbon isotope fractionation of ~1‰. However, the difference between equilibrium pressures in the 12CO2–H2O and 13CO2–H2O systems was smaller than the standard uncertainties of measurement; more accurate pressure measurement is required for quantitative discussion.

scholarly journals Wine origin authentication linked to terroir – wine fingerprint

2019 ◽  
Vol 15 ◽  
pp. 02033
Author(s):  
B. Gabel
Keyword(s):  
Pore Water ◽  
Isotope Composition ◽  
Food Product ◽  
Isotopic Signature ◽  
Original Method ◽  
Economic Problem ◽  
Red Wines ◽  
Table Grapes ◽  
Mineral Phases

Global wine and alcohol trade faces a serious economic problem linked to counterfeiting of these commodities. Recently applied authentication methods and techniques pose more difficulties for counterfeiters but they are apparently not effective once we consider economical losses identified by EU legal authorities. The presented solution links isotopic characteristics of the soil, plant, technological intermediate product and the final food product (wine, grapes) on the basis of 87Sr/86Sr isotopes ratios. For the isotopic signature of wines, the average isotope composition of the substrate cannot be a reliable indicator. Only the isotopic composition of pore water can, as it leaches various mineral phases at different stages and passes into vine root system. Instead of complicated sampling of pore water, an original method of preparing and processing soil samples and consequently must & wine samples was developed. Based on both, soil and biological material analysis, we can unquestionably determine not only geographical but also regional and local authenticity of the wine. Determination of red wines isotopic signature is more straightforward process in comparison to white wines, because of technologically different processing of grapes. That is the reason why, in case of white vines, the 87Sr/86Sr ratio of bentonites (natural purifier and absorbent useful in the process of winemaking) must also be taken into consideration. Results of analyses of Slovak wines from geographically diverse regions as well as from sites in close-by distances have clearly established reliability of presented concept, in which the soil is linked to the plant and to the final food product (wine or table grapes).

Using stable Mg isotopes to distinguish dolomite formation mechanisms: A case study from the Peru Margin

2014 ◽  
Vol 385 ◽  
pp. 84-91 ◽  
Author(s):  
Vasileios Mavromatis ◽  
Patrick Meister ◽  
Eric H. Oelkers
Keyword(s):  
Formation Mechanisms ◽  
Mg Isotopes ◽  
Dolomite Formation

Dissolution and recrystallization in modern shelf carbonates: evidence from pore water and solid phase chemistry

1993 ◽  
Vol 344 (1670) ◽  
pp. 27-36 ◽  
Keyword(s):  
Organic Matter ◽  
Pore Water ◽  
Solid Phase ◽  
Chemical Exchange ◽  
Isotope Composition ◽  
Geochemical Data ◽  
Carbonate Sediments ◽  
Pore Waters ◽  
Carbonate Minerals ◽  
Carbonate Production

We present an overview of geochemical data from pore waters and solid phases that clarify earliest diagenetic processes affecting modern, shallow marine carbonate sediments. Acids produced by organic matter decomposition react rapidly with metastable carbonate minerals in pore waters to produce extensive syndepositional dissolution and recrystallization. Stoichiometric relations among pore water solutes suggest that dissolution is related to oxidation of H 2 S which can accumulate in these low-Fe sediments. Sulphide oxidation likely occurs by enhanced diffusion of O 2 mediated by sulphide-oxidizing bacteria which colonize oxic/anoxic interfaces invaginating these intensely bioturbated sediments. Buffering of pore water stable isotopic compositions towards values of bulk sediment and rapid 45 Ca exchange rates during sediment incubations demonstrate that carbonate recrystallization is a significant process. Comparison of average biogenic carbonate production rates with estimated rates of dissolution and recrystallization suggests that over half the gross production is dissolved and/or recrystallized. Thus isotopic and elemental composition of carbonate minerals can experience significant alteration during earliest burial driven by chemical exchange among carbonate minerals and decomposing organic matter. Temporal shifts in palaeo-ocean carbon isotope composition inferred from bulk-rocks may be seriously compromised by facies-dependent differences in dissolution and recrystallization rates.

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.

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