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.
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.
The snowball Earth hypothesis postulates that the planet was entirely covered by ice for millions of years in the Neoproterozoic era, in a self-enhanced glaciation caused by the high albedo of the ...ice-covered planet. In a hard-snowball picture, the subsequent rapid unfreezing resulted from an ultra-greenhouse event attributed to the buildup of volcanic carbon dioxide (CO(2)) during glaciation. High partial pressures of atmospheric CO(2) (pCO2; from 20,000 to 90,000 p.p.m.v.) in the aftermath of the Marinoan glaciation (∼635 Myr ago) have been inferred from both boron and triple oxygen isotopes. These pCO2 values are 50 to 225 times higher than present-day levels. Here, we re-evaluate these estimates using paired carbon isotopic data for carbonate layers that cap Neoproterozoic glacial deposits and are considered to record post-glacial sea level rise. The new data reported here for Brazilian cap carbonates, together with previous ones for time-equivalent units, provide estimates lower than 3,200 p.p.m.v.--and possibly as low as the current value of ∼400 p.p.m.v. Our new constraint, and our re-interpretation of the boron and triple oxygen isotope data, provide a completely different picture of the late Neoproterozoic environment, with low atmospheric concentrations of carbon dioxide and oxygen that are inconsistent with a hard-snowball Earth.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The Late Jurassic deposits of the Boulonnais area (N-France) represents the proximal lateral-equivalent of the Kimmeridge Clay Formation; they accumulated on a clastic-dominated ramp subject to ...synsedimentary faulting in relation with the northward propagation of the Atlantic rifting. Within the terrigenous accumulations, some carbonate objects are visible at various conspicuous levels: oyster patch reefs and fine-grained carbonate beds, either continuous, or more or less nodular. Preliminary studies demonstrated that the carbonate beds of the Bancs Jumeaux Formation as well as the carbonate matrix of the oyster patch reefs are of diagenetic origin. In this paper, we extend the study to many other limestone beds of the Boulonnais with mud- or wackestone texture, examining facies and microfacies through various techniques as well as geochemical data (O, C and S stable isotopes, major and trace elements). We conclude that all examined carbonate bodies are of early diagenetic origin and that they precipitated at, or close to, the sea bed, from seawater mixing with ascending fluids containing isotopically light carbon of organic origin. Fluid circulation was probably induced by the extensional block-faulting segmentation of the northern margin of the Boulonnais Basin in Late Jurassic times. Fluid seepages were either channelized along fault planes or more diffuse, as illustrated by the model we propose.
•Fine-grained carbonate beds and patch reefs in clastic-dominated sediments.•These carbonate bodies formed during earliest diagenesis.•Carbonate precipitation induced by cold seeps.•Fluid expulsions controlled by synsedimentary tectonics.
The Late Jurassic deposits of the Boulonnais area (N-France) represent the proximal lateral-equivalent of the Kimmeridge Clay Formation; they accumulated on a clastic-dominated ramp subject to ...synsedimentary faulting as a result of the Atlantic Ocean rifting. In the Gris-Nez Cape area, i.e., close to the northern border fault zone of the Jurassic basin, the Late Jurassic sequence contains small-dimensioned oyster patch reefs (<1 m) that are specifically observed at the base of an abrupt deepening trend in the depositional sequence induced by well-defined pulses of normal fault activity. Petrographic analysis of these patch reefs shows that they are exclusively composed of Nanogyra nana embedded in a microsparitic calcite matrix. ™13C measurements, carried out within both the matrix and the shells, display significantly lower values in the matrix compared to the oyster shells which suggests that the carbonate matrix precipitation was involving a carbon source different from marine dissolved inorganic carbon, most probably related to sulfate reduction, which is evidenced by light ™34S in pyrites. Similarities but also differences with lucinid-rich bioconstructions, namely, the Late Jurassic pseudo-bioherms of Beauvoisin (SE-France) suggest that the patch reefs developed at hydrocarbon seeps are related to synsedimentary faults. The extensional block-faulting segmentation of the northern margin of the Boulonnais Basin in Late Jurassic times is thus believed to have induced a sort of small-dimension hydrocarbon seepage field, recorded by the patch reef distribution.
•The Late Jurassic of the Boulonnais (N-France) includes oyster patch reefs.•The reefs were induced by 13C-depleted fluids.•Fluid expulsion was linked to synsedimentary fault activity.
The Early Triassic is generally portrayed as a time of various, high ecological stresses leading to a delayed biotic recovery after the devastating end-Permian mass extinction. This interval is ...notably characterized by repeated biotic crises (e.g., during the late Smithian), large-scale fluctuations of the global carbon, nitrogen and sulfur cycles as well as harsh marine conditions including a combination of ocean acidification, anoxia, extreme seawater temperatures and shifting productivity. Observations from different paleolatitudes suggest that sulfidic (H2S-rich) conditions may have developed widely during the Early Triassic, possibly reaching up to ultra-shallow environments in some places. However, the existence and the spatio-temporal extent of such redox swings remain poorly constrained. In order to explore Early Triassic paleoceanographic redox changes and their potential influences on the biotic recovery, we analyzed multiple sulfur isotopes (32S, 33S, 34S, and 36S) of sedimentary pyrite and carbonate associated sulfate (δ34SCAS) from the Mineral Mountains section, Utah. Sediments from this section were mainly deposited in shallow waters and span the Smithian and lower Spathian. We report a 68‰ range of variations in δ34Spy associated with Δ33Spy varying from −0.01‰ to +0.12‰, whereas the δ34SCAS varies between +19.5‰ and + 34.8‰. We interpret the observed signal of multiple sulfur isotopes as reflecting the operation of pore-water synsedimentary microbial sulfate reduction in open system with respect to sulfates before the late Smithian, evolving to a closed system, sulfate limited, Rayleigh-type distillation across the Smithian/Spathian boundary (SSB) and immediately after the SSB. We argue that this marked change is driven by the effectiveness of the connection between the sedimentary pore waters and the overlying water column, which is, in this case, controlled by the local sedimentological conditions such as the bioturbation intensity and the sedimentation rate. Therefore, our results suggest that changes in the sulfur cycle before and across the SSB at Mineral Mountains is probably a local consequence of the loss of the mixed sedimentary layer during the late Smithian extinction event, as opposed to reflecting the development of a lethal anoxic ocean at the global scale.
Triple oxygen isotope (∆17O with δ18O) signals of H2O and O2 found in sulfate of oxidative weathering origin offer promising constraints on modern and ancient weathering, hydrology, atmospheric gas ...concentrations, and bioproductivity. However, interpretations of the sulfate-water-O2 system rely on assuming fixed oxygen-isotope fractionations between sulfate and water, which, contrastingly, are shown to vary widely in sign and amplitude. Instead, here we anchor sulfate-water-O2 triple oxygen isotope systematics on the homogeneous composition of atmospheric O2 with empirical constraints and modeling. Our resulting framework does not require a priori assumptions of the O2- versus H2O‑oxygen ratio in sulfate and accounts for the signals of mass-dependent and mass-independent fractionation in the ∆17O and δ18O of sulfate's O2‑oxygen source. Within this framework, new ∆17O measurements of sulfate constrain ~2.3 Ga Paleoproterozoic gross primary productivity to between 6 and 160 times present-day levels, with important implications for the biological carbon cycle response to high CO2 concentrations prevalent on the early Earth.
The end of the Neoproterozoic Era (1000 to 541 Ma) is widely believed to have seen the transition from a dominantly anoxic to an oxygenated deep ocean. This purported redox transition appears to be ...closely linked temporally with metazoan radiation and extraordinary perturbations to the global carbon cycle. However, the geochemical record of this transition is not straightforward, and individual data sets have been variably interpreted to indicate full oxygenation by the early Ediacaran Period (635 to 541 Ma) and deep ocean anoxia persevering as late as the early Cambrian. Because any change in marine redox structure would have profoundly impacted nitrogen nutrient cycling in the global ocean, the N isotope signature of sedimentary rocks (δ15Nsed) should reflect the Neoproterozoic deep-ocean redox transition. We present new N isotope data from Amazonia, northwest Canada, northeast Svalbard, and South China that span the Cryogenian glaciations (∼750 to 580 Ma). These and previously published data reveal a N-isotope distribution that closely resembles modern marine sediments, with a mode in δ15N close to +4‰ and range from −4 to +11‰. No apparent change is seen between the Cryogenian and Ediacarian. Data from earlier Proterozoic samples show a similar distribution, but shifted slightly towards more negative δ15N values and with a wider range. The most parsimonious explanation for the similarity of these N-isotope distribution is that as in the modern ocean, nitrate (and hence O2) was stable in most of the middle–late Neoproterozoic ocean, and possibly much of Proterozoic Eon. However, nitrate would likely have been depleted in partially restricted basins and oxygen minimum zones (OMZs), which may have been more widespread than in the modern ocean.
•New δ15Nsed data for 750–580 Ma old sediments from four Neoproterozoic basins.•Distribution of 750–580 Ma δ15Nsed data resembles that of modern oceans.•It is distinct from that of ocean anoxic events.•This suggests the oceans were pervasively oxygenated by 750 Ma.
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