Petrography and geochemistry of carbonate rocks of the Paleoproterozoic Zaonega Formation, Russia : Documentation of C-13-depleted non-primary calcite

The Norwegian Research Council grant 191530/V30 to V.A. Melezhik fully funded the work of AEC, VAM and AL. ATB was supported by NERC grant NE/G00398X/1 to AEF and ARP. We are grateful for sample preparation and analyses to all the personnel at NGU lab. We appreciate the work on carbon and oxygen isotope analyses by Julie Dougans and Chris Taylor. Bojan Otoničar organized and helped with the CL work at the Karst Research Institute at Postojna. Arrangement of TOC, IC, and TC analyses at University of Münster is acknowledged to Harald Strauss.Peer reviewedPostprin

Redox fluctuations, trace metal enrichment and phosphogenesis in the ~2.0 Ga Zaonega Formation

The ~2.0 Ga Zaonega Formation (ZF) holds one of the oldest phosphorites in the geologic record, reaching >15% P2O5. Understanding the depositional conditions that enabled sedimentary phosphorus enrichment in this unit will thus help us to interpret the significance of the temporal distribution of phosphorites in Earth’s early history. Here we use an array of major and trace element data to constrain the redox conditions in the water column and extent of basinal restriction during deposition of the ZF. We also present new selenium (Se) abundance and isotopic data to provide firmer constraints on fluctuations across high redox potentials, which might be critical for phosphogenesis. We find that Se isotope ratios shift over a range of ~3‰ in the ZF, with the earliest stratigraphically-resolved negative Se isotope excursion in the geologic record, implying at least temporarily suboxic waters in the basin. Furthermore, we find that redox-sensitive element (RSE) enrichments coincide with episodes of P enrichment, thereby implicating a common set of environmental controls on these processes. Together, our dataset implies deposition under a predominantly anoxic water column with periodic fluctuations to more oxidizing conditions because of connections to a large oxic reservoir containing Se oxyanions (and other RSE’s, as well as sulfate) in the open ocean. This is broadly consistent with the depositional setting of many modern and recent phosphorites, thereby tying these ancient deposits to a common depositional mechanism. In light of these data, we propose that the broader prevalence of phosphogenesis in the Paleoproterozoic Era was driven by growth of the seawater oxidant reservoir (namely sulfate), thus enabling diagenetic apatite precipitation in basins with high rates of export production, particularly by facilitating the activity of sulfide-oxidizing bacteria. This suggests that the muted authigenic P burial observed in marginal, marine siliciclastic sedimentary rocks during other intervals of the Precambrian was not merely a result of low dissolved P levels in the global deep ocean, but also was influenced by sulfate scarcity and strongly reducing bottom-water conditions

Hydrothermal regeneration of ammonium as a basin-scale driver of primary productivity

Funding: This study was financially supported by a NERC research grant (NE/V010824/1), and Estonian Science Agency project PRG447 to K.KHydrothermal vents are important targets in the search for life on other planets due to their potential to generate key catalytic surfaces and organic compounds for biogenesis. Less well studied, however, is the role of hydrothermal circulation in maintaining a biosphere beyond its origin. Here we explored this question with analyses of organic carbon, nitrogen abundances, and isotopic ratios from the Paleoproterozoic Zaonega Formation (2.0 Ga), NW Russia, which is composed of interbedded sedimentary and mafic igneous rocks. Previous studies have documented mobilization of hydrocarbons, likely associated with magmatic intrusions into unconsolidated sediments. The igneous bodies are extensively hydrothermally altered. Our data reveal strong nitrogen enrichments of up to 0.6 wt.% in these altered igneous rocks, suggesting that the hydrothermal fluids carried ammonium concentrations in the millimolar range, which is consistent with some modern hydrothermal vents. Further, large isotopic offsets of approximately 10 ‰ between organic-bound and silicate-bound nitrogen are most parsimoniously explained by partial biological uptake of ammonium from the vent fluid. Our results, therefore, show that hydrothermal activity in ancient marine basins can provide a locally high flux of recycled nitrogen. Hydrothermal nutrient recycling may thus be an important mechanism for maintaining a large biosphere on anoxic worlds.PostprintPeer reviewe

Carbonate deposition in the Palaeoproterozoic Onega basin from Fennoscandia : a spotlight on the transition from the Lomagundi-Jatuli to Shunga events

Date of Acceptance: 08/05/2015 Date of online publication: 16/05/2015 Acknowledgements Elemental and isotopic data, thin and polished sections used in this contribution were obtained through two large umbrella-projects with grants provided by the Norwegian Research Council grant 191530/V30 to VAM and NERC grant NE/G00398X/1 to AEF. We thank A. Črne, the editor A. Strasser as well as one anonymous reviewer and D. Papineau for providing their valuable criticism and suggestions.Peer reviewedPostprin

Multiple Palaeoproterozoic carbon burial episodes and excursions

Organic-rich rocks (averaging 2–5% total organic carbon) and positive carbonate-carbon isotope excursions (View the MathML source and locally much higher, i.e. the Lomagundi-Jatuli Event) are hallmark features of Palaeoproterozoic successions and are assumed to archive a global event of unique environmental conditions following the c. 2.3 Ga Great Oxidation Event. Here we combine new and published geochronology that shows that the main Palaeoproterozoic carbon burial episodes (CBEs) preserved in Russia, Gabon and Australia were temporally discrete depositional events between c. 2.10 and 1.85 Ga. In northwest Russia we can also show that timing of the termination of the Lomagundi-Jatuli Event may have differed by up to 50 Ma between localities, and that Ni mineralisation occurred at c. 1920 Ma. Further, CBEs have traits in common with Mesozoic Oceanic Anoxic Events (OAEs); both are exceptionally organic-rich relative to encasing strata, associated with contemporaneous igneous activity and marked by organic carbon isotope profiles that exhibit a stepped decrease followed by a stabilisation period and recovery. Although CBE strata are thicker and of greater duration than OAEs (100 s of metres versus metres, ∼106 years versus ∼105 years), their shared characteristics hint at a commonality of cause(s) and feedbacks. This suggests that CBEs represent processes that can be either basin-specific or global in nature and a combination of circumstances that are not unique to the Palaeoproterozoic. Our findings urge circumspection and re-consideration of models that assume CBEs are a Deep Time singularity

Effects of early marine diagenesis and site-specific depositional controls on carbonate-associated sulfate : insights from paired S and O isotopic analyses

Acknowledgment is made to the donors of the American Chemical Society Petroleum Research Fund (#57548-ND2) to D.F. for partial support of this research and from the Estonian Research Council (#PUT611, #PRG836) to O.H and A.L.Carbon, sulfur and oxygen isotope profiles in Silurian strata of the Baltoscandian Basin (Estonia), coincident with the Ireviken Bioevent, provide insights into basin-scale and platform-specific depositional processes. Paired carbon isotope records preserve a positive isotope excursion during the early Wenlock, coincident with faunal turnover, yet δ13C variability of this excursion compared to other locations within the paleobasin reflects local depositional influences superimposed on a global signal. In comparison, sulfur isotope records do not preserve a systematic isotopic excursion over the same interval. Instead, sulfur isotope records have high sample-to-sample stratigraphic variability, particularly in shallow-water carbonate rocks (scatter up to ~10‰ for δ34SCAS and ~ 25‰ for δ34Spyr). This pattern of isotopic variability is also found between sites from the same carbonate platform, where the magnitude and isotopic variability in δ34SCAS and δ34Spyr differ depending on relative local sea level (and therefore facies). Such facies-dependent variability reflects more closed- versus more open-system diagenetic conditions where pulses of increased sedimentation rate in the shallow water environments generates greater isotopic variability in both δ34SCAS and δ34Spyr. Increased reworking and proximity to the shoreline results in local sulfide oxidation, seen as a decrease in δ34SCAS in the most proximal settings. Platform-scale evolution of isotopically distilled pore-fluids associated with dolomitization results in increased δ34SCAS in deep water settings. Correlations in paired δ34SCAS-δ18OCAS data support these conclusions, demonstrating the local alteration of CAS during deposition and early marine diagenesis. We present a framework to assess the sequence of diagenetic and depositional environmental processes that have altered δ34SCAS and find that δ34S of ~27–28‰ approximates Silurian seawater sulfate. Our findings provide a mechanism to understand the elevated variability in many deep-time δ34SCAS records that cannot otherwise be reconciled with behavior of the marine sulfate reservoir.PostprintPeer reviewe

Oxygenated conditions in the aftermath of the Lomagundi-Jatuli Event : the carbon isotope and rare earth element signatures of the Paleoproterozoic Zaonega Formation, Russia

This study was supported by Estonian Research Council project PRG447, and the Estonian Centre of Analytical Chemistry. K.P. and A.L. were supported by the Research Council of Norway through its Centres of Excellence funding scheme grant No. 223259. K.P. acknowledges the Estonian Research Council grant MOBJD542 and T.M. PUT611.The c. 2.0 Ga Zaonega Formation of the Onega Basin (NW Russia) has been central in efforts to understand what led to the initial rise (Great Oxidation Event, GOE) and postulated fall in free atmospheric oxygen and associated high-amplitude carbon cycle excursions, the Lomagundi-Jatuli Event (LJE) and subsequent Shunga Event during Paleoproterozoic time. The Formation accumulated shortly after the LJE and encompasses both the recovery in the carbon cycle and hypothesised contraction of the oceanic oxidant pool. However, interpreting the correct environmental context recorded by geochemical signatures in the Zaonega rocks is difficult due to a complex depositional and diagenetic history. In order to robustly constrain that history, we undertook a multiproxy study (mineralogy, petrography, carbon isotope and rare earth element composition) of carbonate beds in the upper part of the Zaonega Formation recovered in the 102-m composite section of the OnZap drill-cores. Our findings differentiate primary environmental signatures from secondary overprinting and show that: (i) the best-preserved carbonate beds define an upwards increasing δ13Ccarb trend from c. -5.4‰ to near 0‰; and that (ii) large intra-bed δ13Ccarb variations reflect varying contributions of methanotrophic dissolved inorganic carbon (DIC) to the basinal DIC pool. Rare earth element and yttrium (REYSN) patterns confirm a marine origin of the carbonate beds whereas a consistent positive EuSN anomaly suggests a strong high temperature hydrothermal input during accumulation of the Zaonega Formation. Importantly, the presence of a negative CeSN anomaly in the REYSN pattern indicates an oxygenated atmosphere-ocean system shortly after the LJE and indicates that models invoking a fall in oxygen at that time require reassessment.PostprintPeer reviewe

Hydrothermal dedolomitisation of carbonate rocks of the Paleoproterozoic Zaonega Formation, NW Russia — Implications for the preservation of primary C isotope signals

This study was supported by Estonian Science Agency project PUT696 and PRG447, and Estonian Centre of Analytical Chemistry. K.P. and A.L. were supported by the Research Council of Norway through its Centres of Excellence funding scheme grant No. 223259.The Paleoproterozoic Zaonega Formation in Karelia, NW Russia, has played a key role in understanding the environmental conditions postdating the Great Oxidation and Lomagundi-Jatuli Events. Its carbonate- and organic-rich rocks (shungite) define the postulated Shunga Event representing an accumulation of very organic-rich sediments at c. 2 Ga and are central in ideas about changing ocean-atmosphere composition in the wake of those worldwide biogeochemical phenomena. Our work focussed on a key interval of carbonate rocks in the upper part of the Formation to: (i) obtain new high-resolution carbon, oxygen and strontium isotope data complemented by detailed petrography and mineralogical characterisation and (ii) expand upon previous studies by using our data to constrain geochemical modelling and show in greater detail how magmatic hydrothermal fluids induced dedolomitisation and altered geochemical signals. Our findings show that the δ13Ccarb of calcite-rich intervals are the most altered, with values between −16.9 to 0.6‰, whereas the dolomite-dominated parts retain the best-preserved (i.e. most original) values. Those define a trend of steadily increasing δ13Ccarb, from −6 to +0.5‰, which we interpret as a return to normal marine conditions and carbonate‑carbon values following the Lomagundi-Jatuli Event.PostprintPeer reviewe

A refined late-Cryogenian – Ediacaran Earth history of South China: : phosphorous-rich marbles of the Dabie and Sulu orogens

This research was supported by the National Natural Science Foundation of China Grant Numbers 41473039 and 4151101015, and by the Estonian Science Agency project PUT0696.The late-Cryogenian – Ediacaran geological framework for South China is constructed principally from sedimentary successions preserved in the central and western regions of the Yangtze Block. New stratigraphic and carbonate-carbon isotope data allow us to extend that framework into the exhumed HP-UHP subduction complexes of the eastern Dabie and Sulu orogens that separate the South and North China cratons. Those data show that marble and phosphorous-rich (P-rich) units in those complexes were originally part of an Ediacaran shallow-marine shelf-carbonate platform. The basal pebbly schist (metadiamictite) and lowermost P-rich marble of the Jinping Formation (Haizhou Group) in the Sulu Orogen matches in both facies character and C-isotope profile that of the Marinoan-equivalent glacial-cap carbonate couplet of the Nantuo and Doushantuo formations. The Daxinwu Formation (Susong Group) in the eastern Dabie Orogen contains a marble unit that has, for several hundreds of metres, a strikingly uniform C-isotope profile of low δ13C positive values and is overlain by a P-rich graphitic schist; these features match those of the late Ediacaran to early Cambrian Dengying Formation. These correlations establish that the HP-UHP metasedimentary rocks, many of which were once considered to be Palaeo- to Mesoproterozoic in age, are a Neoproterozoic-age cover sequence of the continental margin of the Yangtze Block. Further, their widespread development limits their utility as indicators of offset across the Tan-Lu fault zone and, instead, favours tectonic models that interpret that feature as a continental-scale tear fault formed during the Mesozoic collision and suturing of the North and South China cratons.PostprintPeer reviewe

Geochronology of sediment cores from the Vefsnfjord, Norway

The sedimentary environment is a repository and carrier for a variety of pollutants, and sediment transport from land to coastal areas is an important environmental process. In the present study, we use 210Pb/226Ra and 137Cs in sediment cores to assess sediment supply rates at four sites within the Vefsnfjord in Nordland county, Norway. This area was highly affected by fallout from the Chernobyl accident in 1986 and inventories of 137Cs in the fjord are much higher than in many other Norwegian fjords. Sedimentation rates between 0.042 and 0.25 g cm−2 y−1 (0.060 and 0.38 cm y−1) were determined using a combination of the Constant Rate of Supply (CRS) and Constant Flux:Constant Sedimentation rate (CF:CS) models. Well-defined 137Cs concentration peaks were used as a supplementary tool to the 210Pb dating methods.publishedVersio