Ocean redox structure across the Late Neoproterozoic Oxygenation Event: A nitrogen isotope perspective

International audienceThe 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 Nisotope 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 Nisotopedistribution 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

Large trilobites in a stress-free Early Ordovician environment

International audienceUnderstanding variations in body-size is essential for deciphering the response of an organism to its surrounding environmental conditions and its ecological adaptations. In modern environments, large marine animals are mostly found in cold waters. However, numerous parameters can influence body size variations other than temperatures, such as oxygenation, nutrient availability, predation, or physical disturbances by storms. Here, we investigate trilobite size variations in the Lower Ordovician Fezouata Shale deposited in a cold water environment. Trilobite assemblages dominated by small-to normal-sized specimens that are few cm in length are found in proximal and intermediate settings, while those comprising larger taxa more than 20cm in length are found in the most distal environment of the Fezouata Shale. Drill core material from distal settings shows that sedimentary rocks hosting large trilobites preserved in-situ are extensively bioturbated with a high diversity of trace fossils, indicating that oxygen and nutrients were available in this environment. In intermediate and shallow settings, bioturbation is less extensive and shallower in depth. The rarity of storm events (minimal physical disturbance) and the lack of predators in deep environments in comparison to shallower settings would have also helped trilobites attain larger body sizes. This highly resolved spatial study investigating the effects of numerous biotic and abiotic parameters on body size has wider implications for the understanding of size fluctuations over geological time

Biological Soil Crusts as Modern Analogues for the Archean Continental Biosphere: Insights from Carbon and Nitrogen Isotopes

5 pagesInternational audienceStable isotope signatures of elements related to life such as carbon and nitrogen can be powerful biomarkers that provide key information on the biological origin of organic remains and their paleoenvironments. Marked advances have been achieved in the last decade in our understanding of the coupled evolution of biological carbon and nitrogen cycling and the chemical evolution of the early Earth thanks, in part, to isotopic signatures preserved in fossilized microbial mats and organic matter of marine origin. However, the geologic record of the early continental biosphere, as well as its evolution and biosignatures, is still poorly constrained. Following a recent report of direct fossil evidence of life on land at 3.22 Ga, we compare here the carbon and nitrogen isotopic signals of this continental Archean biosphere with biosignatures of cyanobacteria biological soil crusts (cyanoBSCs) colonizing modern arid environments. We report the first extended δ13C and δ15N data set from modern cyanoBSCs and show that these modern communities harbor specific isotopic biosignatures that compare well with continental Archean organic remains. We therefore suggest that cyanoBSCs are likely relevant analogs for the earliest continental ecosystems. As such, they can provide key information on the timing, extent, and possibly mechanism of colonization of the early Earth's emergent landmasses

Microbial and diagenetic steps leading to the mineralisation of Great Salt Lake microbialites.

12 pagesInternational audienceMicrobialites are widespread in modern and fossil hypersaline environments, where they provide a unique sedimentary archive. Authigenic mineral precipitation in modern microbialites results from a complex interplay between microbial metabolisms, organic matrices and environmental parameters. Here, we combined mineralogical and microscopic analyses with measurements of metabolic activity in order to characterise the mineralisation of microbial mats forming microbialites in the Great Salt Lake (Utah, USA). Our results show that the mineralisation process takes place in three steps progressing along geochemical gradients produced through microbial activity. First, a poorly crystallized Mg-Si phase precipitates on alveolar extracellular organic matrix due to a rise of the pH in the zone of active oxygenic photosynthesis. Second, aragonite patches nucleate in close proximity to sulfate reduction hotspots, as a result of the degradation of cyanobacteria and extracellular organic matrix mediated by, among others, sulfate reducing bacteria. A final step consists of partial replacement of aragonite by dolomite, possibly in neutral to slightly acidic porewater. This might occur due to dissolution-precipitation reactions when the most recalcitrant part of the organic matrix is degraded. The mineralisation pathways proposed here provide pivotal insight for the interpretation of microbial processes in past hypersaline environments

Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth

International audienceThe terminal Neoproterozoic Era (850–542 Ma) is characterized by the most pronounced positive sulfur isotope (34 S/ 32 S) excursions in Earth's history, with strong variability and maximum values averaging d 34 SB þ 38%. These excursions have been mostly interpreted in the framework of steady-state models, in which ocean sulfate concentrations do not fluctuate (that is, sulfate input equals sulfate output). Such models imply a large pyrite burial increase together with a dramatic fluctuation in the isotope composition of marine sulfate inputs, and/or a change in microbial sulfur metabolisms. Here, using multiple sulfur isotopes (33 S/ 32 S, 34 S/ 32 S and 36 S/ 32 S ratios) of carbonate-associated sulfate, we demonstrate that the steady-state assumption does not hold in the aftermath of the Marinoan Snowball Earth glaciation. The data attest instead to the most impressive event of oceanic sulfate drawdown in Earth's history, driven by an increased pyrite burial, which may have contributed to the Neoproterozoic oxygenation of the oceans and atmosphere

In situ carbon and oxygen isotopes measurements in carbonates by fiber coupled laser diode-induced calcination

Stable isotopic compositions of carbon and oxygen (δ13C et δ18O) measured from carbonates are used in geology to reconstruct paleotemperatures and to learn about the evolution of the biogeochemical carbon cycle. The standard technique used since the middle of the XXth century [1] to measure isotopic ratios is based on a wet chemical protocol which CO2 is evolved from the acidic dissolution of carbonates followed by quantification of CO2 molecules isotopologues using mass spectrometer or infrared spectroscopy. This is a lengthy protocol that necessitate to manipulate acid solution and numerous gas phases purification steps before isotopic measurements. Our new preparation technique aims at offering an alternative to the wet chemical preparation of the samples by using a direct extraction of CO2 via a laser-induced calcination process. In addition to save time, this method allows to consider spatially resolved and automated in-situ measurements and does not necessitate further purification steps of the evolved CO2 during calcination

Natural stable isotopes ratios and associated elemental concentrations of sediment core PRGL 1-4 from the Gulf on Lion

Natural stable isotopes ratios (d13Corg and d15N) and associated elemental concentrations (i.e. total organic carbon and total nitrogen contents) preserved in marine sediments are frequently used for the determination of paleoenvironmental processes such as the organic-matter origin. Previous studies highlighted bias in the determination of such geochemical proxies due to pre-analysis acid treatment methods. This study is the first systematic comparison of the effect of acid treatment methods on bulk organic-matter using a unique sedimentary system, under glacial and interglacial conditions. We used the common method for pre-treatment analysis, which consists of acidification of bulk sediment followed by several de-ionised water rinses. We investigated the effect of acid type (i.e. Hydrochloric acid and Acetic acid), but also strength (from 0.2 to 10 mol/l) on the d13Corg, d15N, TOC, TN and C/N ratio on three samples from the Gulf of Lion. Two (i.e. S.302 and S.102) were deposited during glacial maxima whereas S.157 characterizes interglacial conditions. Samples d13Corg values range between -21.7 and -24.4 per mil with TOC varying from 0.56 and 0.84 %wt/wt. d15N values is more stable with an average value of 3.0 ± 0.1 per mil with a TN average of 0.08 ± 0.002 %wt/wt. We show that acid type did not significantly affect results. We also find that (i) glacial and interglacial samples do not react similarly to acid pre-treatment, (ii) high acid strength (>1.5 mol/l) induce significant bias on d13Corg values, TOC values and therefore on C/N ratio; (iii) 25% of an isotopically distinct pool of organic carbon was lost between the use of 0.2 mol/l and 1.5 mol/l affecting d13Corg values by more than 1.5 per mil; (iv) geochemical evidences indicate that the leachable organic-carbon pool is preferentially composed of terrestrial organic-matter. These findings call for precautions when using C/N ratios and associated d13Corgvalues for paleoenvironmental and climate reconstructions

Distribution spatio-temporelle des gisements à préservation exceptionnelle dans l’Ordovicien inférieur de la région de Zagora (Maroc)

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Constraining the rise of oxygen with oxygen isotopes.

10 pagesInternational audienceAfter 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 ∆33S up to + 1.55‰ and low δ18O 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 δ18O and high ∆33S in sulfates

In Situ carbon and oxygen isotopes measurements in carbonates using laser-induced calcination: A step forward field isotopic characterization

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