Phosphorus is a nutrient fundamental to life and when it precipitates in modern environments bacteria are intimately involved in its release, concentration, and mineralization. Preserved fossil ...bacteria in phosphate crusts and grains from the ca. 1850 million-year-old Bijiki Iron Formation Member of the Michigamme Formation, Michigan provide insight into the longevity and nature of this relationship. The Michigamme Formation accumulated near the end of the Earth's initial phosphogenic episode (ca. 2.2 and 1.8Ga) to produce one of the first granular phosphorites. Phosphatic lithofacies consist of fine- to medium-sand-sized francolite peloids concentrated on bedding surfaces in peritidal facies. Granular beds are up to 2cm thick and peloids are often partially to completely replaced by dolomite and chert. The grains contain organic matter and pyrite framboids that suggest bacterial breakdown of organic matter and bacterial sulfate reduction.
The peritidal nature of phosphorite in the Michigamme Formation is in sharp contrast to Phanerozoic phosphogenic environments in deeper coastal upwelling settings. Peritidal settings were well suited for phosphogenesis under the very low oxygen and low dissolved sulfate levels of the Paleoproterozoic as cyanobacteria produced oxygen in shallow water and evaporation led to increased sulfate concentrations. Such concomitant processes helped establish focused redox interfaces in the sediment that chemosynthetic bacterial communities (sulfur oxidizers, reducers, forms that concentrate P, and possibly iron oxidizers) could exploit. Phosphate released from organic matter by heterotrophic bacteria and Fe-redox pumping was further concentrated by these chemotrophs; a process that forms late Neoproterozoic to Phanerozoic phosphorites but on a much larger scale.
This early example of a granular phosphorite demonstrates that, like their Phanerozoic counterparts, Paleoproterozoic phosphorites are the concentrated indirectly biomineralized products of bacterial communities. But unlike younger analogs, which accumulated across subtidal shelves and shelf margins, these ancient deposits formed only in tidal flat settings where phosphogenic redox processes could be established in the sediment. From this early beginning, the zone of phosphogenesis likely migrated into deeper water settings as oxygen and sulfate levels rose, expanding the zone of chemosynthetic bacterial and associated phosphogenesis across the shelf.
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•Chemosynthetic organisms caused phosphate mineralization.•Chemosynthetic bacteria create and exploit redox conditions in near-shore settings.•Phosphate mineralization began in Paleoproterozoic peritidal settings.•Post-middle Neoproterozoic this microbial-sedimentary system shifted to deep water.•Francolite is a signpost for early life in Proterozoic marine sedimentary rocks.
Dolomite cement is a significant and widespread component of Phanerozoic sucrosic dolomites. Cements in dolomites that were never deeply buried are limpid, have planar faces (non-saddle forms), often ...distinct zonation in cathodoluminescence and form syntaxial overgrowths on crystals facing pores. Five samples of sucrosic dolomites, interpreted as having had mostly lime-mudstone or wackestone precursors in four carbonate aquifers, provide insights into the abundance of planar cements in sucrosic dolomites. Such cement comprises 11% to 45% (32% mean) of peritidal to sub-tidal dolomites on an outcrop in the Edwards aquifer (Early Cretaceous) of central Texas; 19% to 33% (25% mean) of ramp dolomites in the Hawthorn Group (Oligo-Miocene) and 50% to 70% in shelf dolomites of the Avon Park Formation (Eocene) in the Upper Floridan aquifer of sub-surface peninsular Florida; 18% to 45% (32+% mean) of sub-tidal shelf dolomites in quarry sections of the Burlington-Keokuk Formation (Early Mississippian) in south-eastern Iowa; and 18% to 76% (50% mean) in shallow cores and outcrops of outer-shelf dolomites from the Gambier Limestone (Oligo-Miocene) of South Australia. Backstripping the cement phases revealed by cathodoluminescence colour photomicrographs documents the effects of cements on textural coarsening, pore-space reduction, induration and general 'maturation' of these dolomites. Most pre-Holocene dolomites are multiphase crystalline rocks composed of: (i) seed crystals or 'cores'; (ii) crystal cortices that concentrically enlarged the cores; and (iii) free-space, syntaxial precipitates of limpid cement around the crystals. Remaining CaCO₃ grains and micrite can be replaced by dolomite, but typically they are dissolved between stages (ii) and (iii), creating systems of intercrystal and mouldic pores typical of sucrosic dolomites. Networks of cement overgrowths, aided by water-filled pore systems under hydrostatic to lithostatic pressure, are judged to slow or prevent compaction in sucrosic dolomites. It can be argued that cortex growth involves both replacement of CaCO₃ particles and microcementation of their interparticle pores. This interpretation, and the abundance of cements in so many dolomites, would obviate the controversy over the volumetrics of 'replacement dolomitization'. Limpid, planar and syntaxial dolomite cements of early diagenetic origin are interpreted to have precipitated from clear pore waters, at low temperatures (<30 to 35 °C) and shallow burial depths (<100 m), in water-saturated networks of dolomite 'silt' and 'sand'. Cements in many dolomites in island and continental-aquifer systems appear to result from event-driven processes related to sea-level highstands. Cementation events can follow 'replacement dolomitization' events by time intervals ranging from geologically 'instantaneous' to tens of million years.
The Palaeoproterozoic Baraga Group (ca. 1850
±
1
Ma) of northern Michigan is a ∼
1200
m thick sedimentary succession of marine clastic, iron formation, chert, and phosphatic sedimentary rocks that ...accumulated at the peak of the world's first major phosphogenic episode. Lithofacies stacking patterns are interpreted to record the flooding of the Nuna continental margin during two sea-level cycles. The base of the first sequence is marked by a transgressive lag on Archean basement that is transitional into a highstand accumulation of sandstones deposited in peritidal environments. The bottom of the second sequence is characterized by a chert and carbonate unit with numerous subaerial exposure surfaces deposited in intertidal to supratidal environments. This chert grades upward into subtidal deposits composed of interbedded organic-rich mudstone and sandstone. The highstand and falling stage systems tracts are composed of progradational deltaic deposits. Sequences were framed using the newly discovered Sudbury impact ejecta horizon as a datum. Its emplacement approximately coincides with unrelated environmental changes that increased the delivery of river-borne sediment to the Nuna margin.
Iron bearing minerals ankerite, siderite, and pyrite show that ferrous iron was present in peritidal to deep marine environments. Ankerite dominates nearshore settings where pyrite is absent; pyrite occurs in deeper, progradational deltaic deposits where sulfide was produced by bacterial sulfate reduction. Phosphorite is restricted to shallow-water sediments of the first sequence and the lowstand of the second sequence. Precipitation is interpreted to be the result of Fe-redox pumping just below the sediment–water interface where photosynthetically-produced, nearshore oxygen oases impinged on the seafloor. Such shallow-water phosphorite accumulation is in stark contrast to many Phanerozoic depositional systems in which phosphogenesis occurs across the shelf. This difference likely reflects the dissimilarity in the oxygenation state of the seafloor. In the Precambrian, Fe-redox pumping and thus, phosphogenesis, was restricted to shallow-water settings with a suboxic seafloor. In the Phanerozoic, phosphorite forms in the full spectrum of shelf environments because the entire seafloor is generally well oxygenated. The concentration of bioavailable P in neritic environments during the Proterozoic may have played a major role in the development of benthic microbial ecosystems and evolving eukaryotes.
The Matoush uranium deposit is situated in the Paleoproterozoic Otish Basin, northern Quebec, Canada, and is hosted by the Indicator Formation sandstones. Its sheet-like ore bodies are closely ...associated with the steeply dipping Matoush Fracture, which hosts mafic dykes and minor quartz–feldspar–tourmaline pegmatites. Regional diagenesis, involving oxidizing basinal fluids (δ
2
H ∼−15‰, δ
18
O ∼8‰), produced mostly illite and possibly leached U from accessory phases in the Indicator Formation sandstones. The bimodal Matoush dyke intruded the Indicator Formation along the Matoush Fracture, and the related metasomatism produced Cr-rich dravite and muscovite in both the dyke and the proximal sandstones. Uraninite formed when U
6+
in the basinal brine was reduced to U
4+
in contact with the mafic dyke and by Fe
2+
in Cr–dravite and Cr–muscovite, and precipitated together with eskolaite and hematite. Because of its unique characteristics, the Matoush deposit cannot be easily classified within the generally accepted classification of uranium deposits. Two of its main characteristics (unusual reduction mechanism, structural control) do not correspond to the sandstone-hosted group of deposits (unconformity type, tabular, roll front), in spite of uranium being derived from the Otish Group sandstones.
The Palaeoproterozoic Frere Formation (ca 1.89 Gyr old) of the Earaheedy Basin, Western Australia, is a ca 600 m thick succession of iron formation and fine‐grained, clastic sedimentary rocks that ...accumulated on an unrimmed continental margin with oceanic upwelling. Lithofacies stacking patterns suggest that deposition occurred during a marine transgression punctuated by higher frequency relative sea‐level fluctuations that produced five parasequences. Decametre‐scale parasequences are defined by flooding surfaces overlain by either laminated magnetite or magnetite‐bearing, hummocky cross‐stratified sandstone that grades upward into interbedded hematite‐rich mudstone and trough cross‐stratified granular iron formation. Each aggradational cycle is interpreted to record progradation of intertidal and tidal channel sediments over shallow subtidal and storm‐generated deposits of the middle shelf. The presence of aeolian deposits, mud cracks and absence of coarse clastics indicate deposition along an arid coastline with significant wind‐blown sediment input. Iron formation in the Frere Formation, in contrast to most other Palaeoproterozoic examples, was deposited almost exclusively in peritidal environments. These other continental margin iron formations also reflect upwelling of anoxic, Fe‐rich sea water, but accumulated in the full spectrum of shelf environments. Dilution by fine‐grained, windblown terrigenous clastic sediment probably prevented the Frere iron formation from forming in deeper settings. Lithofacies associations and interpreted paragenetic pathways of Fe‐rich lithofacies further suggest precipitation in sea water with a prominent oxygen chemocline. Although essentially unmetamorphosed, the complex diagenetic history of the Frere Formation demonstrates that understanding the alteration of iron formation is a prerequisite for any investigation seeking to interpret ocean‐atmosphere evolution. Unlike studies that focus exclusively on their chemistry, an approach that also considers palaeoenvironment and oceanography, as well the effects of post‐depositional fluid flow and alteration, mitigates the potential for incorrectly interpreting geochemical data.
Ediacaran phosphorites capture the dynamics of the ultimate biolimiting nutrient, phosphorus, during perhaps the most critical transition of Earth's climatic and ecological history. Concomitant with ...the Neoproterozoic Oxygenation Event was the deposition of the first extensive phosphorites across marine shelves, typically interpreted as a basinward shift in the locus of phosphogenesis facilitated by deep-ocean oxygenation. Petrographic and spectroscopic analyses of proximal phosphorites from the Ediacaran Doushantuo Formation near the Yangtze Gorges area of South China reveal the presence of interlaminated pristine, muddy, and granular phosphorites that were cemented by early diagenetic iron phosphate, an additional, previously undocumented seafloor P sink. Transmitted- and reflected-light microscopy, cathodoluminescence microscopy, and back-scattered electron scanning electron microscopy were used to reconstruct the paragenesis of phosphorites at the Wanjiagou section near Zhangcunping (Hubei Province) and demonstrate that pristine phosphorite precipitated authigenically as francolite via microbially-mediated phosphogenesis as evidenced by preserved microbial laminations along with filamentous and coccoidal microfossils. Subsequent tidal reworking of pristine hardgrounds and phosphatic mudstones produced minimally-coated intraclasts and peloidal phosphatic grains that were cemented by iron phosphate soon after deposition but before compaction. Raman spectroscopy, bulk-sample and micro-X-ray diffractometry indicate the iron phosphate cement is composed of phosphosiderite/strengite (Fe+3PO4•2H2O). The presence of phosphosiderite can be attributed to either syndepositional oxidation of phosphorites or thermal stabilization of vivianite (Fe2+3(PO4)2•8H2O). In both cases, the occurrence of phosphosiderite represents the first direct evidence for iron phosphate minerals as a P sink during the Ediacaran and suggests phosphogenesis may have partially proceeded in ferruginous porewaters in contrast to the redox-independent process of francolite precipitation. Integration of petrographic and geochemical techniques, such as those employed in this study, offers the ability to corroborate P speciation analyses and provides an independent determination of P phase partitioning. Ultimately, this approach is paramount in testing hypotheses that suggest ferrous iron phosphate minerals played a regulatory role in global Proterozoic oxygenation.
•Petrographic, Raman, and XRD data of Ediacaran Doushantuo phosphorite in South China.•First report of Fe phosphate from Ediacaran phosphorite.•Fe phosphate likely derived from early diagenetic vivianite cement.•Fe phosphate was a phosphorus sink in Ediacaran oceans.
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•Transition out of one of the most extreme global ice ages in Earth history.•Sub-sea ice microbial marine ecosystem on the cusp of oxygenation.•Short-term redox fluctuations allowed ...phosphate to precipitate on the seafloor.•Photosynthesis and oxygen limited by ice cover during the Marinoan Snowball Earth.
Termination of the Marinoan Snowball Earth ice age (635 Ma) marked the transition to a greenhouse world. This climate change forever modified the biogeochemical cycling of iron and phosphorus, ended large-scale iron formation deposition, began accumulation of phosphorus on marine shelves, and led to the Ediacaran radiation of eukaryotes. The Jacadigo Basin, Brazil, contains a nearly complete record of this critical transition.
Glaciomarine diamictites and iron formation accumulated during two Marinoan ice advances with hydrothermal input of iron delivered via ice-margin upwelling. Biochemically precipitated rhythmites of siderite, sedimentary apatite, and hematite represent microbially mediated, sub-sea ice precipitation. Siderite laminae preserve microbial textures and have a mean ∂13C = −8.80‰, PDB (+/−0.86‰) reflecting degradation of organic matter at the seafloor. These millimeter-scale rhythmites are a sensitive record of sub-ice dynamics because they formed in response to short-term fluctuations of O2 due to seasonal sub-ice photosynthesis. They demonstrate the connection between ice cover, O2, and cycling of iron and nutrient elements such as phosphorus.
These biochemical rhythmites suggest that Cryogenian sea ice limited oxygen production prior to the onset of the Neoproterozoic Oxygenation Event. O2 increased enough to concentrate bioavailable phosphorus at the seafloor, which was essential for later diversification of metazoans in the Ediacaran. Such sub-ice Cryogenian biochemical systems may provide Earth-based analogs for life on ice-covered worlds, such as Europa and Enceladus.
The Thelon Basin, Nunavut, Canada, is host to unconformity-type uranium mineralisation and has the potential to host other economic deposits. The Thelon Formation (ca. 1750 Ma) is composed of thick ...(meters to tens of meters), poorly sorted, trough cross-bedded conglomerate and coarse-grained lithic arenite beds, and to a lesser extent, well-sorted, medium- to coarse-grained quartz arenite beds. Relatively rare, 1–12 cm thick, clay-rich siltstones to fine-grained sandstone layers punctuate the coarser lithofacies. Based on regional analysis of drill cores and outcrops, multiple unconformity-bounded sequences are defined in this fluvial-dominated sedimentary succession. Stratigraphic correlations are based on detailed lithofacies analysis, distinct changes in fining-upward cycle thickness, and intraformational surfaces (unconformities, transgressive surfaces, and paleosols).
Diagenetic and paragenetic relationships vary systematically with sedimentology and stratigraphy of the Thelon and provide a framework for understanding the evolution of fluid-flow systems in the context of basin hydrostratigraphy. Stratigraphic units with well-sorted textures, which lacked clay and unstable framework grains, originally were aquifers (depositional aquifers) during early basin evolution. However, pervasive, early quartz cementation radically reduced the porosity and permeability of these units, occluding pore throats and transforming them into aquitards. Proximal fluvial and alluvial fan lithofacies that contained detrital, mechanically infiltrated, and diagenetic clay minerals and/or unstable detrital grains originally had low permeabilities and only experienced minor quartz cementation. In the deep burial setting (2–7 km), these units retained sufficient permeability to allow diagenetic fluid flow (diagenetic aquifers) as suggested by feldspar dissolution, quartz dissolution, and formation and recrystallization of illite and other diagenetic reactions. Tracing potential diagenetic aquifer and aquitard units across the study area allowed development of a hydrostratigraphic model. In this model, diagenetic aquifers onlap onto, and focused basinal fluids into basement rocks to the east in the Thelon Basin (in the vicinity of the Kiggavik uranium deposit).
The ephemeral nature of most sedimentation processes and the fragmentary character of the sedimentary record are of first-order importance. Despite a basic uniformity of external controls on ...sedimentation resulting in markedly similar lithologies, facies, facies associations and depositional elements within the rock record across time, there are a number of secular changes, particularly in rates and intensities of processes that resulted in contrasts between preserved Precambrian and Phanerozoic successions. Secular change encompassed (1) variations in mantle heat, rates of plate drift and of continental crustal growth, the gravitational effects of the Moon, and in rates of weathering, erosion, transport, deposition and diagenesis; (2) a decreasing planetary rotation rate over time; (3) no vegetation in the Precambrian, but prolific microbial mats, with the opposite pertaining to the Phanerozoic; (4) the long-term evolution of the hydrosphere–atmosphere–biosphere system. A relatively abrupt and sharp turning point was reached in the Neoarchaean, with spikes in mantle plume flux and tectonothermal activity and possibly concomitant onset of the supercontinent cycle. Substantial and irreversible change occurred subsequently in the Palaeoproterozoic, whereby the dramatic change from reducing to oxidizing volcanic gases ushered in change to an oxic environment, to be followed at ca. 2.4–2.3Ga by the “Great Oxidation Event” (GOE); rise in atmospheric oxygen was accompanied by expansion of oxygenic photosynthesis in the cyanobacteria. A possible global tectono-thermal “slowdown” from ca. 2.45–2.2Ga may have separated a preceding plate regime which interacted with a higher energy mantle from a ca. 2.2–2.0Ga Phanerozoic-style plate tectonic regime; the “slowdown” period also encompassed the first known global-scale glaciation and overlapped with the GOE. While large palaeodeserts emerged from ca. 2.0–1.8Ga, possibly associated with the evolution of the supercontinent cycle, widespread euxinia by ca. 1.85Ga ushered in the “boring billion” year period. A second time of significant and irreversible change, in the Neoproterozoic, saw a second major oxidation event and several low palaeolatitude Cryogenian (740–630Ma) glaciations. With the veracity of the “Snowball Earth” model for Neoproterozoic glaciation being under dispute, genesis of Pre-Ediacaran low-palaeolatitude glaciation remains enigmatic. Ediacaran (635–542Ma) glaciation with a wide palaeolatitudinal range contrasts with the circum-polar nature of Phanerozoic glaciation. The observed change from low latitude to circum-polar glaciation parallels advent and diversification of the Metazoa and the Neoproterozoic oxygenation (ca. 580Ma), and was succeeded by the Ediacaran–Cambrian transition which ushered in biomineralization, with all its implications for the chemical sedimentary record.
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► Provides overview of secular change in global sedimentation patterns. ► Abrupt, sharp turning points in Earth evolution at Neoarchaean and Neoproterozoic. ► Substantial and irreversible change from Palaeoproterozoic and Neoproterozoic oxidation events.
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