Nitrogen isotope compositions in sedimentary rocks (d15Nsed) are routinely used for reconstructing Cenozoic N-biogeochemical cycling and are also being increasingly applied to understanding the ...evolution of ancient environments. Here we review the existing knowledge and rationale behind the use of d15Nsed as a proxy for the Precambrian N-biogeochemical cycle with the aims of (i) identifying the major uncertainties that affect analyses and interpretation of nitrogen isotopes in ancient sedimentary rocks, (ii) developing a framework for interpreting the Precambrian d15Nsed record, (iii) testing this framework against a database of Precambrian d15Nsed values compiled from the literature, and (iv) identifying avenues of focused research that should increase confidence in interpreting Precambrian d15Nsed data. This review highlights the intrinsic complexity of the d15Nsed proxy and the significant effort that remains to realize its potential. Specifically, it is crucial to gain a better understanding of how and when diagenesis and metamorphism affect the d15N of bulk and kerogen-bound nitrogen. Ultimately, more data are required to apply statistics to interpreting d15Nsed variability within given geological time intervals. Finally, numerical modeling of the d15Nsed variability expected in different environments under varying redox scenarios is necessary to establish a predictive template for interpreting the ancient nitrogen isotope record. In spite of the challenges facing the application of this proxy to the Precambrian, the existing d15Nsed record shows several features possibly related to the stepwise oxygenation of the surface environment, underlining the potential for nitrogen isotopes to reveal clues about the evolution of early Earth.
Core-mantle differentiation is the largest event experienced by a growing planet during its early history. Terrestrial core segregation imprinted the residual mantle composition by scavenging ...siderophile (iron-loving) elements such as tungsten, cobalt and sulphur. Cosmochemical constraints suggest that about 97% of Earth's sulphur should at present reside in the core, which implies that the residual silicate mantle should exhibit fractionated (34)S/(32)S ratios according to the relevant metal-silicate partition coefficients, together with fractionated siderophile element abundances. However, Earth's mantle has long been thought to be both homogeneous and chondritic for (34)S/(32)S, similar to Canyon Diablo troilite, as it is for most siderophile elements. This belief was consistent with a mantle sulphur budget dominated by late-accreted chondritic components. Here we show that the mantle, as sampled by mid-ocean ridge basalts from the south Atlantic ridge, displays heterogeneous (34)S/(32)S ratios, directly correlated to the strontium and neodymium isotope ratios (87)Sr/(86)Sr and (143)Nd/(144)Nd. These isotope trends are compatible with binary mixing between a low-(34)S/(32)S ambient mantle and a high-(34)S/(32)S recycled component that we infer to be subducted sediments. The depleted end-member is characterized by a significantly negative δ(34)S of -1.28 ± 0.33‰ that cannot reach a chondritic value even when surface sulphur (from continents, altered oceanic crust, sediments and oceans) is added. Such a non-chondritic (34)S/(32)S ratio for the silicate Earth could be accounted for by a core-mantle differentiation record in which the core has a (34)S/(32)S ratio slightly higher than that of chondrites (δ(34)S = +0.07‰). Despite evidence for late-veneer addition of siderophile elements (and therefore sulphur) after core formation, our results imply that the mantle sulphur budget retains fingerprints of core-mantle differentiation.
Carbonado is a unique type of polycrystalline diamond characterised, among others, by
13C-depleted isotope compositions (δ
13C
∼
-25‰ vs. PDB), little advanced nitrogen aggregation (Ib-IaA) and ...sintered (ceramic-like) diamond grains. Its origin remains an enigma, with models proposing a formation either in the Earth's crust or even within an exploding super-nova. The possibility that carbonado formed in the Earth's mantle is often rejected because diamond with carbonado-like geochemical features has never been found in rocks, such as kimberlites, that carry diamonds from the mantle.
In this study, it is shown that the C- and N- stable isotope compositions, nitrogen contents and nitrogen speciation of diamonds from the Dachine komatiite (French Guyana) exhibit unambiguous similarities with carbonados. These include C-isotopes (from -32.6 to +
0.15‰, mode at ∼-27‰), N-aggregation (only Ib-IaA diamonds, from 2 to 76% of N-pairs) and N-isotopes (from -4.1 to +
6.9‰, average ∼ +
2.1
±
2.9‰), which all strikingly match the carbonado data. This evidence illustrates that the main geochemical arguments usually called to reject a mantle origin of carbonado are no longer valid. A model linking carbonado crystallisation from komatiite volatiles is developed. In this model, the sintering is produced by the high temperature of the komatiite magma thus accounting for their absence in colder kimberlites. The low δ
13C compositions of carbonados would be inherited from the transition zone (> 300
km depths), which is known to yield diamonds with distinct C-isotope distributions compared to most lithospheric diamonds (150–300
km depths). This model can account for most available observations of carbonados, including their large size, sintering, photoluminescense/cathodoluminescence features and geochemical characteristics.
To better address how subducted protoliths drive the Earth's mantle sulfur isotope heterogeneity, we report new data for sulfur (S) and copper (Cu) abundances, S speciation and multiple S isotopic ...compositions (32S, 33S, 34S, 36S) in 15 fresh submarine basaltic glasses from the Samoan archipelago, which defines the enriched-mantle-2 (EM2) endmember.
Bulk S abundances vary between 835 and 2279 ppm. About 17±11% of sulfur is oxidized (S6+) but displays no consistent trend with bulk S abundance or any other geochemical tracer. The S isotope composition of both dissolved sulfide and sulfate yield homogeneous Δ33S and Δ36S values, within error of Canyon Diablo Troilite (CDT). In contrast, δ34S values are variable, ranging between +0.11 and +2.79‰ (±0.12‰ 1σ) for reduced sulfur, whereas oxidized sulfur values vary between +4.19 and +9.71‰ (±0.80‰, 1σ). Importantly, δ34S of the reduced S pool correlates with the 87Sr/86Sr ratios of the glasses, in a manner similar to that previously reported for South-Atlantic MORB, extending the trend to δ34S values up to +2.79±0.04‰, the highest value reported for undegassed oceanic basalts.
As for EM-1 basalts from the South Atlantic ridge, the linear δ34S–87Sr/86Sr trend requires the EM-2 endmember to be relatively S-rich, and only sediments can account for these isotopic characteristics. While many authors argue that both the EM-1 and EM-2 mantle components record subduction of various protoliths (e.g. upper or lower continental crust, lithospheric mantle versus intra-metasomatized mantle, or others), it is proposed here that they primarily reflect sediment recycling. Their distinct Pb isotope variation can be accounted for by varying the proportion of S-poor recycled oceanic crust in the source of mantle plumes.
•Sulfide segregation under a coexistence of dissolved sulfides and sulfates.•34S/32S for dissolved sulfides is correlated to the 87Sr/86Sr of the glasses relative abundance of sulfate is not buffered in the melt.•EM-1 and EM-2 mantle endmembers must share a common sedimentary nature.
We report the quadruple sulfur isotope compositions, sulfur contents and speciation major and trace elements (including copper and chlorine abundances) of eleven basalts collected in the Garrett ...transform fault. We combine these data to discuss the absence of S isotopic fractionation along both partial melting and low-pressure fractional crystallization.
The variations of K2O/TiO2 and La/SmN-ratios (respectively between 0.017 and 0.067, and between 0.31 and 0.59) suggest a range of depletion in Garrett lavas that includes ultra depleted samples (K2O/TiO2<0.03). The remarkable level of incompatible element depletion is consistent with re-melting of a depleted source. Contrasting with incompatible element depletion, all samples display similar S and Cu abundance (at a given major-element composition) to mid-ocean ridge basalts (MORB). This indicates that Garrett Intra Transform Lavas (ITL) are sulfide saturated as MORB are. Copper content for Garrett parental melts (MgO >8%) are ∼80 ppm, indistinguishable from MORBs. This requires their mantle sources, variably depleted in incompatible element, to host residual sulfide buffering the Cu content of all erupted melts. We calculate a minimum S content for the source of ultra-depleted Garrett lavas of 100±40ppmS, i.e. roughly a factor of 2 below the MORB mantle source.
After exclusion of a single sample with Cl/K ratio >0.1 that likely experienced hydrothermal sulfide assimilation, Garrett ITLs display homogeneous δ34S, Δ33S and Δ36S values with averages of −0.68±0.08‰, +0.010±0.005‰ and −0.04±0.04‰, respectively (all 1σ, n=10). The δ34S values display no relationship with either K2O/TiO2 variations or extent sulfide fractionation. From these observations, we derive a 34S/32S fractionation factor between exsolved sulfides and sulfide dissolved in silicate melts of 1.0000±0.0003. The S isotopic fractionation during partial melting can thus be considered as negligible, and both MORBs and ITLs record the 34S/32S ratio of their mantle source.
The concept of sulfide melts segregating from the mantle, sinking and being added to the core during planetary differentiation was termed the ‘Hadean Matte’. The segregation of sulfides from the mantle to the core during planetary differentiation could account for various geochemical features of the Earth's mantle. Based on S isotopic mass balance, we derive a lower and upper limit for the hadean matte. While the lower bound corresponds to a virtually negligible hadean matte, the upper limit is 3.36×1024gS (i.e. ∼10% of the bulk terrestrial S), which remains 5 to 10 times lower than previous estimates. This upper bound nonetheless requires high mantle S content >1000 ppm S before the extraction of the hadean matte. This suggestion would have chronological requirements, requiring any sulfide melt to have formed after the core extraction but before late accretion of the highly siderophile elements.
•Garrett lavas show ultra depletion in incompatible element, consistent with re-melting.•Constant δ34S values, indicating that S isotopes are insensitive to partial melting processes.•This allows estimating a sulfide-silicate melt S isotopic fractionation to be 0.0±0.3‰.•An upper limit for the S amount in the hadean matte is 3.36×1024gS (i.e. ∼10% of the bulk terrestrial S).
After permanent atmospheric oxygenation, anomalous sulfur isotope compositions were lost from sedimentary rocks, demonstrating that atmospheric chemistry ceded its control of Earth's surficial sulfur ...cycle to weathering. However, mixed signals of anoxia and oxygenation in the sulfur isotope record between 2.5 to 2.3 billion years (Ga) ago require independent clarification, for example via oxygen isotopes in sulfate. Here we show <2.31 Ga sedimentary barium sulfates (barites) from the Turee Creek Basin, W. Australia with positive sulfur isotope anomalies of ∆
S up to + 1.55‰ and low δ
O down to -19.5‰. The unequivocal origin of this combination of signals is sulfide oxidation in meteoric water. Geochemical and sedimentary evidence suggests that these S-isotope anomalies were transferred from the paleo-continent under an oxygenated atmosphere. Our findings indicate that incipient oxidative continental weathering, ca. 2.8-2.5 Ga or earlier, may be diagnosed with such a combination of low δ
O and high ∆
S in sulfates.
Diamond, as the deepest sample available for study, provides a unique opportunity to sample and examine parts of the Earth’s mantle not directly accessible. In order to provide further constraints on ...mantle convection and deep volatile cycles, we analysed nitrogen and carbon isotopes and nitrogen abundances in 133 diamonds from Juina (Brazil) and Kankan (Guinea). Host syngenetic inclusions within these diamonds indicate origins from the lithosphere, the asthenosphere-transition zone and the lower mantle.
Juina and Kankan diamonds both display overall carbon isotopic compositions within the current upper mantle range but the δ13C signatures of diamonds from the asthenosphere-transition zone extend toward very negative and positive values, respectively. Two Kankan diamonds with both lower mantle and asthenosphere-transition zone inclusions (KK-45 and KK-83) are zoned in δ13C, and have signatures consistent with multiple growth steps likely within both the lower mantle and the asthenosphere-transition zone illustrating the transfer of material through the 670km seismic discontinuity.
At a given locality, diamonds from the upper and the lower mantle show similar δ15N distributions with coinciding modes within the range defined by typical upper mantle samples, as one might expect for a well stirred reservoir resulting from whole mantle convection.
Kankan diamonds KK-11 (lower mantle), KK-21 and KK-92 (both lithospheric) display the lowest δ15N values (-24.9%, -39.4% and -30.4%) ever measured in terrestrial samples, which we interpret as reflecting primordial heterogeneity preserved in an imperfectly mixed convective mantle.
Our diamond data thus provide support for deeply rooted convection cells, together with the preservation of primordial volatiles in an imperfectly mixed convecting mantle, thereby reconciling the conflicting interpretations regarding mantle homogeneity derived from geochemical and geophysical studies.
► Diamonds illustrate large material transfer across the 670km seismic discontinuity. ► Kankan diamonds record the contribution of primordial nitrogen with δ15N<−40‰. ► Primordial heterogeneities either as blobs or as a deeper mantle layer. ► Subducted slabs penetrate into the deep lower mantle.
Unravelling the origin of organic compounds that were accreted into asteroids requires better constraining the impact of asteroidal hydrothermal alteration on their isotopic signatures, molecular ...structures, and spatial distribution. Here, we conducted a multi-scale/multi-technique comparative study of the organic matter (OM) from two CM chondrites (that originate from the same parent body or from identical parent bodies that accreted the same mixture of precursors) and underwent a different degree of hydrothermal alteration: Paris (a weakly altered CM chondrite – CM 2.8) and Murchison (a more altered one – CM 2.5). The Paris insoluble organic matter (IOM) shows a higher aliphatic/aromatic carbon ratio, a higher radical abundance and a lower oxygen content than the Murchison IOM. Analysis of the OM in situ shows that two texturally distinct populations of organic compounds are present within the Paris matrix: sub-micrometric individual OM particles and diffuse OM finely distributed within phyllosilicates and amorphous silicates. These results indicate that hydrothermal alteration on the CM parent body induced aromatization and oxidation of the IOM, as well as a decrease in radical and nitrogen contents. Some of these observations were also reported by studies of variably altered fragment of Tagish Lake (C2), although the hydrothermal alteration of the OM in Tagish Lake was apparently much more severe. Finally, comparison with data available in the literature suggests that the parent bodies of other chondrite petrologic groups could have accreted a mixture of organic precursors different from that accreted by the parent body of CMs.
To better address how Mid-Ocean Ridge Basalt (MORB) sulfur isotope composition can be modified by assimilation and/or by immiscible sulfide fractionation, we report sulfur (S), chlorine (Cl) and ...copper (Cu) abundances together with multiple sulfur isotope composition for 38 fresh basaltic glasses collected on the Pacific–Antarctic ridge. All the studied glasses – with the exception of 8 off-axis samples – exhibit relatively high Cl/K, as the result of pervasive Cl-rich fluid assimilation. This sample set hence offers an opportunity to document both the upper mantle S isotope composition and the effect of hydrothermal fluids assimilation on the S isotope composition of erupted basalts along segments that are devoid of plume influence.
Δ33S and Δ36S yield homogenous values within error of Canyon Diablo Troilite (CDT), whereas δ34S are variable, ranging between −1.57±0.11‰ and +0.60±0.10‰ with a mean value of −0.64±0.40‰ (1σ, versus V-CDT). The geographic distribution of δ34S follows a spike-like pattern, with local 34S-enrichments by up to +1.30‰ compared to a low-δ34S baseline. As hydrothermal massive sulfides are characterized by relative 34S-enrichments, such first-order variability can be accounted for by hydrothermal sulfide assimilation, a process that would occur for a subset of samples (n=10). Excluding these particular samples, the mean δ34S is significantly less variable, averaging at −0.89±0.11‰ (1σ, n=28), a value that we suggest to be representative of the average MORB source value for Pacific–Antarctic basalts. Weak trends between δ34S and 206Pb/204Pb are displayed by such uncontaminated samples suggesting the recycled oceanic crust to have a modest impact on the S budget of the mantle. Their positive signs, however, suggest the depleted mantle to have a δ34S of −1.40±0.50‰. The sub-chondritic 34S/32S value that was previously observed for the South-Atlantic mantle is here extended to the Pacific–Antarctic domain. Such a feature cannot originate from oceanic crust recycling and substantiates the concept of a core–mantle fractionation relict.
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