scholarly journals Strong Isotope-dependent Photodissociation Branching Ratios of N2 and Their Potential Implications for the 14N/15N Isotope Fractionation in Titan's Atmosphere

2021 ◽  
Vol 923 (2) ◽  
pp. 196
Author(s):  
Min Liu ◽  
Pan Jiang ◽  
Liya Lu ◽  
Tonghui Yin ◽  
Liying Ma ◽  
...  

Abstract The origin and evolution of the 14N/15N ratio of Titan’s atmosphere has long been a subject of debate. Clearly a better understanding of the N isotopic fractionation mechanism would greatly help resolve this. Photodissociation of N2 by solar radiation has been suggested to either play a negligible role in fractionating the N isotopes in Titan, due to its rather low escape velocity, or to preferentially remove 15N through self-shielding controlled photochemical reactions. Here, we systematically measure the branching ratios of 14N15N between N(4S)+N(2P) and N(4S)+N(2D) channels. We find that many of its absorption states predominantly dissociate into N(4S)+N(2P) with a strong isotope effect between 14N2 and 14N15N. Since N atoms produced from N(4S)+N(2P) acquire velocities close to Titan’s escape velocity, these findings provide a new N isotope fractionation mechanism for Titan that has not been considered before, potentially providing important constraints on the origin and evolution of Titan’s N2-dominated atmosphere.

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Elaheh Lotfi-Kalahroodi ◽  
Anne-Catherine Pierson-Wickmann ◽  
Olivier Rouxel ◽  
Rémi Marsac ◽  
Martine Bouhnik-Le Coz ◽  
...  

AbstractAlthough redox reactions are recognized to fractionate iron (Fe) isotopes, the dominant mechanisms controlling the Fe isotope fractionation and notably the role of organic matter (OM) are still debated. Here, we demonstrate how binding to organic ligands governs Fe isotope fractionation beyond that arising from redox reactions. The reductive biodissolution of soil Fe(III) enriched the solution in light Fe isotopes, whereas, with the extended reduction, the preferential binding of heavy Fe isotopes to large biological organic ligands enriched the solution in heavy Fe isotopes. Under oxic conditions, the aggregation/sedimentation of Fe(III) nano-oxides with OM resulted in an initial enrichment of the solution in light Fe isotopes. However, heavy Fe isotopes progressively dominate the solution composition in response to their binding with large biologically-derived organic ligands. Confronted with field data, these results demonstrate that Fe isotope systematics in wetlands are controlled by the OM flux, masking Fe isotope fractionation arising from redox reactions. This work sheds light on an overseen aspect of Fe isotopic fractionation and calls for a reevaluation of the parameters controlling the Fe isotopes fractionation to clarify the interpretation of the Fe isotopic signature.


2003 ◽  
Vol 81 (9) ◽  
pp. 1630-1635 ◽  
Author(s):  
Keith A Hobson ◽  
Franz Bairlein

There is currently a great deal of interest in using stable-isotope methods to investigate diet and migratory connections in wild passerines. To apply these methods successfully, it is important to understand how stable isotopes discriminate or change between diet and the tissue of interest and what the element-turnover rates are in metabolically active tissues. Of particular use are studies that sample birds non-destructively through the use of blood and feathers. We investigated patterns of isotopic discrimination between diet and blood and feathers of Garden Warblers (Sylvia borin) raised on an isotopically homogeneous diet (48% C, 5% N) and then switched to one of two experimental diets, mealworms (56.8% C, 8.3% N) and elderberries, Sambucus niger (47.4% C, 1.5% N). We established that the discrimination factors between diet and blood appropriate for stable carbon (δ13C) and nitrogen (δ15N) isotopes are +1.7‰ and +2.4‰, respectively. For feathers, these values were +2.7‰ and +4‰, respectively. Turnover of elemental nitrogen in whole blood was best approximated by an exponential-decay model with a half-life of 11.0 ± 0.8 days (mean ± SD). Corresponding turnover of carbon was estimated to range from 5.0 ± 0.7 to 5.7 ± 0.8 days. We conclude that this decoupling of nitrogen- and carbon-turnover rates can be explained by differences in metabolic routing of dietary macromolecules. Our results suggest that tracking frugivory in migratory passerines that switch diets between insects and fruits may be complicated if only a trophic-level estimate is made using δ15N measurements.


2019 ◽  
Vol 157 (7) ◽  
pp. 1144-1148
Author(s):  
Yingkui Xu ◽  
Dan Zhu ◽  
Xiongyao Li ◽  
Jianzhong Liu

AbstractLaboratory experiments have shown that thermal gradients in silicate melts can lead to isotopic fractionation; this is known as the Richter effect. However, it is perplexing that the Richter effect has not been documented in natural samples as thermal gradients commonly exist within natural igneous systems. To resolve this discrepancy, theoretical analysis and calculations were undertaken. We found that the Richter effect, commonly seen in experiments with wholly molten silicates, cannot be applied to natural systems because natural igneous samples are more likely to be formed out of partially molten magma and the presence of minerals adds complexity to the behaviour of the isotope. In this study, we consider two related diffusion-rate kinetic isotope effects that originate from chemical diffusion, which are absent from experiments with wholly molten samples. We performed detailed calculations for magnesium isotopes, and the results indicated that the Richter effect for magnesium isotopes is buffered by kinetic isotope effects and the total value of magnesium isotope fractionation can be zero or even undetectable. Our study provides a new understanding of isotopic behaviour during the processes of cooling and solidification in natural magmatic systems.


1980 ◽  
Vol 26 (10) ◽  
pp. 1173-1177 ◽  
Author(s):  
R. G. L. McCready ◽  
V. A. Grinenko ◽  
H. R. Krouse

Proteus vulgaris metabolized thiosulfate to H2S. The amount evolved and its sulfur isotope composition identified it solely with sulfane sulfur. In contrast. Salmonella heidelberg sequentially reduced the sulfane sulfur of S2O32− with slight enrichment of the evolved sulfide in 32S and then reduced the sulfonate sulfur of S2O32− with large isotopic selectivities and an inverse isotopic fractionation pattern. The inverse isotope fractionation pattern for the H2S derived from the sulfonate sulfur was almost identical to that observed during the reduction of high concentrations of sulfite by S. heidelberg.


2021 ◽  
Vol 7 (30) ◽  
pp. eabg7775
Author(s):  
Zijie Luo ◽  
Yarui Zhao ◽  
Zhichao Chen ◽  
Yao Chang ◽  
Su-e Zhang ◽  
...  

The deuterium versus hydrogen (D/H) isotopic ratios are important to understand the source of water on Earth and other terrestrial planets. However, the determinations of D/H ratios suggest a hydrogen isotopic diversity in the planetary objects of the solar system. Photochemistry has been suggested as one source of this isotope heterogeneity. Here, we have revealed the photodissociation features of the water isotopologue (HOD) at λ = 120.8 to 121.7 nm. The results show different quantum state populations of OH and OD fragments from HOD photodissociation, suggesting strong isotope effect. The branching ratios of H + OD and D + OH channels display large isotopic fractionation, with ratios of 0.70 ± 0.10 at 121.08 nm and 0.49 ± 0.10 at 121.6 nm. Because water is abundant in the solar nebula, photodissociation of HOD should be an alternative source of the D/H isotope heterogeneity. This isotope effect must be considered in the photochemical models.


2011 ◽  
Vol 7 (2) ◽  
pp. 887-920 ◽  
Author(s):  
J. Xiao ◽  
Y. K. Xiao ◽  
C. Q. Liu ◽  
Z. D. Jin

Abstract. Experiments involving boron incorporation into brucite (Mg(OH)2) from magnesium-free artificial seawater with pH values ranging from 9.5 to 13.0 were carried out to better understand the incorporation behavior of boron into brucite. The results show that both concentration of boron in deposited brucite ([B]d) and its boron partition coefficient (Kd) between deposited brucite and final seawater are controlled by pH of the solution. The incorporation capacity of boron into brucite is much stronger than that into oxides and clay minerals. The isotopic compositions of boron in deposited brucite (δ11Bd) are higher than those in the associated artificial seawater (δ11Bisw) with fractionation factors ranging between 1.0177 and 1.0569, resulting from the preferential incorporation of B(OH)3 into brucite. Both boron adsorptions onto brucite and precipitation reaction of H3BO3 with brucite exist during deposition of brucite from artificial seawater. The simultaneous occurrence of both processes determines the boron concentration and isotopic fractionation of brucite. The isotopic fractionation behaviors and mechanisms of boron incorporated into brucite are different from those into carbonates. Furthermore, the isotopic compositions of boron in modern corals might be affected by the existence of brucite in madrepore and the preferential incorporation of B(OH)3 into brucite. An exploratory study for the influence of brucite on the boron isotopic composition in modern corals is justifiable.


2021 ◽  
Author(s):  
Laura Crick ◽  
Andrea Burke ◽  
William Hutchison ◽  
Stephen Sparks ◽  
Sue Mahony ◽  
...  

<p>The ~74ka Toba eruption in Indonesia was one of the largest volcanic events of the Quaternary and loaded an estimated 100 million tonnes of H<sub>2</sub>SO<sub>4</sub> into the atmosphere. Understanding the precise timing of this colossal eruption is vital to unravelling the climatic and environmental impacts of the largest volcanic events on Earth. Sulfur aerosols injected into the stratosphere following large volcanic events scatter incoming radiation and lead to global cooling, and in the case of Toba it has been suggested that it led to cooling of 1 – 5°C and extinctions of some local hominin populations. One of the most enigmatic features of the Toba eruption is that the S peak has yet to be identified in the ice core records, although numerous candidate sulfate peaks have been identified in both Arctic and Antarctic ice cores. To address this, we analysed the sulfur isotope fingerprint (δ<sup>34</sup>S and Δ<sup>33</sup>S) of 11 Toba candidates from two Antarctic ice cores by multi-collector inductively coupled plasma mass spectrometry. This approach allows us to evaluate injection altitudes and to distinguish large tropical eruptions from proximal eruptions because stratospheric sulfur aerosols undergo UV photochemical reactions that impart a sulfur mass-independent isotopic fractionation (S-MIF). In contrast, tropospheric sulfur aerosols do not exhibit S-MIF because they are shielded from the relevant UV radiation by the ozone layer.</p><p>We identify three stratospheric, tropical eruption candidates with two recording the largest Δ<sup>33</sup>S signals measured to date in the ice core archives. The largest of these Δ<sup>33</sup>S signals is >2 ‰ more negative than previous measurements of the 1257 Samalas eruption (the largest eruption of the last 2000 years), despite having a similar integrated sulfate flux for this event to the ice core. These three candidates are within uncertainly of the Ar<sup>40</sup>/Ar<sup>39 </sup>age estimates for the Toba eruption and when considered with other paleoclimate proxies place the event during the transition into Greenland Stadial 20.  Finally, we further analyse the relationship between the Toba eruption candidates and these proxies to determine the precise timing and potential climatic impacts of one of the largest eruptions of the Quaternary period.</p>


2021 ◽  
Author(s):  
Caroline Soderman ◽  
Oliver Shorttle ◽  
Simon Matthews ◽  
Helen Williams

The geochemistry of global mantle melts suggests that both mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) sample lithological and temperature heterogeneities originating in both the upper and lower mantle. Recently, non-traditional stable isotopes have been suggested as a new tool to complement existing tracers of mantle heterogeneity (e.g., major and trace elements, radiogenic isotopes), because mineral- and redox-specific equilibrium stable isotope fractionation effects can link the stable isotope ratios of melts to their source mineralogy and melting degree. Here, we investigate five stable isotope systems (Mg-Ca-Fe-V-Cr) that have shown promise in models or natural samples as tracers of mantle temperature and/or lithological heterogeneity. We use a quantitative model, combining thermodynamically self-consistent mantle melting and equilibrium isotope fractionation models, to explore the behaviour of the isotope ratios of these elements during melting of three mantle lithologies (peridotite, and silica-excess and silica-deficient pyroxenites), responding to changes in mantle mineralogy, oxygen fugacity, temperature and pressure.We find that, given current analytical precision, the stable isotope systems examined here are not predicted to be sensitive to mantle potential temperature variations through equilibrium isotope fractionation processes. By contrast, source lithological heterogeneity is predicted to be detectable in some cases in the stable isotope ratios of erupted basalts, although generally only at proportions of > 10% MORB-like pyroxenite in the mantle source, given current analytical precision. Magnesium and Ca stable isotopes show most sensitivity to a garnet-bearing source lithology, and Fe and Cr stable isotopes are potentially sensitive to the presence of MORB-like pyroxenite in the mantle source, although the behaviour of Cr isotopes is comparatively under-constrained and requires further work to be applied with confidence to mantle melts. When comparing the magnitude and direction of predicted equilibrium isotopic fractionation of peridotite and pyroxenite melts to natural MORB and OIB data, we find that aspects of the natural data (including the mean Mg-Ca-Fe-V isotopic composition of MORB, the range of Mg-Ca isotopic compositions seen in MORB data, the mean Mg-Ca-Cr isotopic composition of OIB, and the range of Mg-V-Cr isotopic compositions in OIB data) can be matched by equilibrium isotope fractionation during partial melting of peridotite and pyroxenite sources -- with pyroxenite required even for some MORB data. However, even when considering analytical uncertainty on natural sample measurements, the range in stable isotope compositions seen across the global MORB and OIB datasets suggests that kinetic isotope fractionation, or processes modifying the isotopic composition of recycled crustal material such that it is distinct from MORB, may be required to explain all the natural data. We conclude that the five stable isotope systems considered here have potential to be powerful complementary tracers to other geochemical tracers of the source lithology of erupted basalts. However, continued improvements in analytical precision in conjunction with experimental and theoretical predictions of isotopic fractionation between mantle minerals and melts are required before these novel stable isotopes can be unambiguously used to understand source heterogeneity in erupted basalts.


2014 ◽  
Vol 11 (13) ◽  
pp. 3707-3719 ◽  
Author(s):  
K. Lalonde ◽  
A. V. Vähätalo ◽  
Y. Gélinas

Abstract. Organic carbon (OC) depleted in 13C is a widely used tracer for terrestrial organic matter (OM) in aquatic systems. Photochemical reactions can, however, change δ13C of dissolved organic carbon (DOC) when chromophoric, aromatic-rich terrestrial OC is selectively mineralized. We assessed the robustness of the δ13C signature of DOC (δ13CDOC) as a tracer for terrestrial OM by estimating its change during the photobleaching of chromophoric DOM (CDOM) from 10 large rivers. These rivers cumulatively account for approximately one-third of the world's freshwater discharge to the global ocean. Photobleaching of CDOM by simulated solar radiation was associated with the photochemical mineralization of 16 to 43% of the DOC and, by preferentially removing compounds depleted in 13C, caused a 1 to 2.9‰ enrichment in δ13C in the residual DOC. Such solar-radiation-induced photochemical isotopic shift could bias the calculations of terrestrial OM discharge in coastal oceans towards the marine end-member. Shifts in terrestrial δ13CDOC should be taken into account when constraining the terrestrial end-member in global calculation of terrestrially derived DOM in the world ocean.


2019 ◽  
Vol 523 ◽  
pp. 191-197 ◽  
Author(s):  
François Robert ◽  
Lambert Baraut-Guinet ◽  
Pierre Cartigny ◽  
Peter Reinhardt

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