Chemostratigraphy of Paleoproterozoic carbonate successions of the Wyoming Craton: tectonic forcing of biogeochemical change?

The Archean Wyoming Craton is flanked on the south and east by belts of Paleoproterozoic supracrustal successions whose correlation is complicated by lack of geochronologic constraints and continuous outcrop. However, carbonate units in these successions may be correlated by integrating carbon isotope stratigraphy with lithostratigraphy. The 10 km thick Paleoproterozoic Snowy Pass Supergroup in the Medicine Bow Mountains was deposited on the present-day southern flank of the Wyoming Craton; it contains three discrete levels of glacial diamictite correlative with those in the Huronian Supergroup, on the southern margin of the Superior Craton. The Nash Fork Formation of the upper Snowy Pass Supergroup is significantly younger than the uppermost diamictite and was deposited after the end of the Paleoproterozoic glacial epoch. Carbonates at the base of the Nash Fork Formation record remarkable ¹³C-enrichment, up to +28‰ (V-PDB), whereas those from overlying members of the lower Nash Fork Formation have δ¹³C values between +6 and +8‰. Carbonates from the upper Nash Fork Formation above the carbonaceous shale have carbon isotope values ranging between 0 and +2.5‰. The transition from high carbon isotope values to those near 0‰ in the Nash Fork Formation is similar to that at the end of the ca. 2.2–2.1 Ga carbon isotope excursion in Fennoscandia. This chemostratigraphic trend and deposition of BIFs, Mn-rich lithologies, carbonaceous shales and phosphorites at the end of the global ca. 2.2–2.1 Ga carbon isotope excursion are likely related to ocean overturn associated with the final breakup of the Kenorland supercontinent. Correlative carbonates from the Slaughterhouse Formation in the Sierra Madre, WY, and from the Whalen Group in the Rawhide Creek area in the Hartville Uplift, WY, have highly positive carbon isotope values. In contrast, carbonates from other exposures of the Whalen Group in the Hartville Uplift and all carbonate units in the Black Hills, SD, have carbon isotope values close to 0‰. Combined with existing geochronologic and stratigraphic constraints, these data suggest that the Slaughterhouse Formation and the succession exposed in the Rawhide Creek area of the Hartville Uplift are correlative with the lower and middle Nash Fork Formation and were deposited during the ca. 2.2–2.1 Ga carbon isotope excursion. The Estes and Roberts Draw formations in the Black Hills and carbonates from other exposures in the Hartville Uplift postdate the ca. 2.2–2.1 Ga positive carbon isotope excursion and are most likely correlative with the upper Nash Fork Formation. The passive margin, on which the carbonates with highly positive carbon isotope values were deposited, extended around the southern flank of the Wyoming Craton through the Sierra Madre, Medicine Bow Mountains and Hartville Uplift. The presence of carbonates with carbon isotope values close to 0‰ in the upper Nash Fork Formation and the Whalen Group indicates that the passive margin persisted on the southern flank of the Wyoming Craton after the carbon isotope excursion. Rifting in the Black Hills, likely related to the final breakup of the Kenorland, succeeded the carbon isotope excursion, since the Estes and Roberts Draw formations, deposited during rifting and ocean opening on the eastern flank of the Wyoming Craton, postdate the carbon isotope excursion.     

Chemostratigraphy of Mesoproterozoic and Neoproterozoic carbonates of the Nico Pérez Terrane,Río de la Plata Craton,Uruguay

Increasing evidence shows that Mesoproterozoic rocks are widespread in the Río de la Plata Craton. Carbon and strontium isotope analyses were carried out for three different, carbonate-bearing successions in the southern Nico Pérez Terrane. The Parque UTE Group is erected, comprising (from base to top) the mainly volcanogenic Cañada Espinillo Formation, the dolomitic Mina Valencia Formation and the mixed carbonate-siliciclastic Cerro del Mástil Formation. A δ¹³C curve was obtained for carbonates of the Parque UTE Group, which is characterized by a plateau at +1 to +1.6‰ V-PDB, bracketed between two negative excursions (−1.8‰ V-PDB at the base and −3.3‰ V-PDB at the top). These values are consistent with a Mesoproterozoic depositional age for the unit, as indicated by U–Pb ages of synsedimentary volcanics and gabbros of 1429 ± 21 and 1492 ± 4 Ma, respectively.     

A review of the stratigraphy and geological setting of the Palaeoproterozoic Magondi Supergroup,Zimbabwe – Type locality for the Lomagundi carbon isotope excursion

The Palaeoproterozoic Magondi Supergroup lies unconformably on the Archaean granitoid-greenstone terrain of the Zimbabwe Craton and experienced deformation and metamorphism at 2.06–1.96 Ga to form the Magondi Mobile Belt. The Magondi Supergroup comprises three lithostratigraphic units. Volcano-sedimentary rift deposits (Deweras Group) are unconformably overlain by passive margin, back-arc, and foreland basin sedimentary successions, including shallow-marine sedimentary rocks (Lomagundi Group) in the east, and deeper-water shelf to continental slope deposits in the west (Piriwiri Group). Based on the upward-coarsening trend and presence of volcanic rocks at the top of the Piriwiri and Lomagundi groups, the Piriwiri Group is considered to be a distal, deeper-water time-equivalent of the Lomagundi Group. The Magondi Supergroup experienced low-grade metamorphism in the southeastern zone, but the grade increases to upper greenschist and amphibolite facies grade to the north along strike and, more dramatically, across strike to the west, reaching upper amphibolite to granulite facies in the Piriwiri Group.     

Chemostratigraphy of the Tamengo Formation (Corumbá Group,Brazil): A contribution to the calibration of the Ediacaran carbon-isotope curve

The Corumbá Group, cropping out in the southern Paraguay Belt in Brazil, is one of the most complete Ediacaran sedimentary archives of palaeogeographic, climatic, biogeochemical and biotic evolution in southwestern Gondwana. The unit hosts a rich fossil record, including acritarchs, vendotaenids (Vendotaenia, Eoholynia), soft-bodied metazoans (Corumbella) and skeletal fossils (Cloudina, Titanotheca). The Tamengo Formation, made up mainly of limestones and marls, provides a rich bio- and chemostratigraphic record. Several outcrops, formerly assigned to the Cuiabá Group, are here included in the Tamengo Formation on the basis of lithological and chemostratigraphical criteria. High-resolution carbon isotopic analyses are reported for the Tamengo Formation, showing (from base to top): (1) a positive δ¹³C excursion to +4‰ PDB above post-glacial negative values, (2) a negative excursion to −3.5‰ associated with a marked regression and subsequent transgression, (3) a positive excursion to +5.5‰, and (4) a plateau characterized by δ¹³C around +3‰. A U-Pb SHRIMP zircon age of an ash bed interbedded in the upper part of the δ¹³C positive plateau yielded 543 ± 3 Ma, which is considered as the depositional age ( Babinski et al., 2008a). The positive plateau in the upper Tamengo Formation and the preceding positive excursion are ubiquitous features in several successions worldwide, including the Nama Group (Namibia), the Dengying Formation (South China) and the Nafun and Ara groups (Oman). This plateau is constrained between 542 and 551 Ma, thus consistent with the age of the upper Tamengo Formation. The negative excursion of the lower Tamengo Formation may be correlated to the Shuram–Wonoka negative anomaly, although δ¹³C values do not fall beyond −3.5‰ in the Brazilian sections. Sedimentary breccias occur just beneath this negative excursion in the lower Tamengo Formation. One possible interpretation of the origin of these breccias is a glacioeustatic sea-level fall, but a tectonic interpretation cannot be completely ruled out.     

High-δ13C Paleoproterozoic Carbonates from the Aravalli Supergroup,Western India

High δ¹³C values up to 11%_PDB occur in Paleoproterozoic dolostones from the Aravalli Supergroup, western India. Correlation of high δ¹³C with high δ¹⁸O up to 23%_SMOW in the studied carbonates suggests that pre-metamorphic δ¹³C values were above 10%_PDB. The data are consistent with worldwide positive excursions in the δ¹³C of marine bicarbonate. The positive excursion was contemporaneous with sedimentation.     

The Paleoproterozoic Wernecke Supergroup of Yukon,Canada: Relationships to orogeny in northwestern Laurentia and basins in North America,East Australia,and China

The Paleoproterozoic Wernecke Supergroup of Yukon was deposited when the northwestern margin of Laurentia was undergoing major adjustments related to the assembly of the supercontinent Columbia (Nuna) from 1.75 to 1.60 Ga. U–Pb detrital zircon geochronology coupled with Nd isotope geochemistry and major and trace element geochemistry are used to characterize the evolution of the Wernecke basin. The maximum depositional age of the Wernecke Supergroup is reevaluated and is estimated at 1649 ± 14 Ma. Detrital zircon age spectra show a bimodal age distribution that reflects derivation from cratonic Laurentia, with a prominent peak at 1900 Ma. Going upsection, the late Paleoproterozoic peak shifts from 1900 Ma to 1850–1800 Ma, and the proportion of Archean and early Paleoproterozoic zircon decreases. These modifications are a consequence of a change in the drainage system in western Laurentia caused by early phase of the Forward orogeny, several hundred km to the east. The exposed lower and middle parts of the Wernecke Supergroup are correlated with the Hornby Bay Group. Zircon younger than 1.75 Ga appear throughout the sedimentary succession and may have originated from small igneous suites in northern Laurentia, larger source regions such as magmatic arc terranes of the Yavapai and early Mazatzal orogenies in southern Laurentia, and possible arc complexes such as Bonnetia that may have flanked the eastern margin of East Australia. Basins with similar age and character include the Tarcoola Formation (Gawler Craton) and the Willyama Supergroup (Curnamona Province) of South Australia, the Isan Supergroup of North Australia, and the Dongchuan–Dahongshan–Hondo successions of southeast Yangtze Craton (South China). Nd isotope ratios of the Wernecke Supergroup are comparable with values from Proterozoic Laurentia, the Isan and Curnamona assemblages of east Australia, the Gawler Craton, and the Dahongshan–Dongchuan–Hondo successions of the Yangtze Craton of South China. These similarities are compelling evidence for a shared depositional system among these successions. Western Columbia in the Late Paleoproterozoic may have had a dynamic SWEAT-like configuration involving Australia, East Antarctica and South China moving along western Laurentia.     

Petrology,geochemistry and fluid inclusion studies of Cu-Au mineralization in paleoproterozoic Salumber-Ghatol belt,Aravalli Supergroup,Rajasthan

The Salumber-Ghatol belt in Rajasthan, India, situated along southern margin of the Aravalli Craton, hosts a cluster of Cu-Au deposits in calcitic and dolomitic marbles that belong to Debari Group of the Paleo-mesoproterozoic Aravalli Supergroup. The Fe-Mn rich dolomitic marble of the Delwara Formation hosts Cu-Au-Fe-oxide mineralization at Ghagri and associated distal K-Fe-Mg rich altered rocks (cryptocrystalline microcline + magnesioriebeckite + magnetite + phlogopite) and proximal feldspathised carbonate rocks (medium grained albite + microcline + dolomite + magnetite). The calcitic marble of Mukandpura Formation hosts Dugocha Cu-Au deposit with development of distal graphitetourmaline-bearing albitites and proximal albite-microcline-magnetite rocks. Calcite and dolomite carbonates of Bhukia region with development of albite-actinolite-bearing alteration assemblages host the largest of the Cu-Au deposits in this belt. The second generation folds and associated ductile-brittle shear zones of the multiply deformed events constitute conduits for the mineralizing fluids at all locations in this belt.     

Response to the Lomagundi-Jatuli Event in the southwestern margin of the Yangtze Plate: Evidence from the carbon and oxygen isotopes of the Paleoproterozoic Yongjingshao Formation

The Lomagundi-Jatuli Event (LJE) refers to the significant positive carbon isotope excursion in seawater constituents that occurred immediately after the increase in atmospheric oxygen content during the Paleoproterozoic (2.22–2.06 Ga). The δ¹³C values of 46 dolostone samples collected from the Paleoproterozoic Yongjingshao Formation varied in the range of 0.05 ‰–4.95 ‰ (V-PDB; maximum: 4.95‰) in this study, which may be related to the multicellular eukaryotes in the Liangshan Formation in the Yimen Group. They are much higher than the δ¹³C values of marine carbonates (?1.16‰ on average). The δ¹³C values of other formations in the Paleoproterozoic Yimen Group are negative. The notable positive carbon isotope anomalies of the Yongjingshao Formation indicate the response to the LJE at the southwestern margin of the Yangtze Block, which is reported for the first time. Furthermore, they are comparable to the δ¹³C values of carbonates in the Dashiling Formation of the Hutuo Group in the Wutaishan area in the North China Craton, the Wuzhiling Formation of the Songshan Group in the Xiong’ er area, Henan Province, and the Dashiqiao Formation of the Liaohe Group in the Guanmenshan area, Liaoning Province. Therefore, it can be further concluded that the LJE is a global event. This study reveals that LJE occurred in Central Yunnan at 2.15–2.10 Ga, lasting for about 50 Ma. The macro-columnar, bean-shaped, and microfilament fossils and reticular ultramicrofossils of multicellular eukaryotes in this period were discovered in the Liangshan Formation of the Yimen Group. They are the direct cause for the LJE and are also the oldest paleontological fossils ever found. The major events successively occurring in the early stage of the Earth include the Great Oxygenation Event (first occurrence), the global Superior-type banded iron formations (BIFs), the Huronian glaciation, the Great Oxygenation Event (second occurrence), the explosion of multicellular eukaryotes, the positive carbon isotope excursion, and the global anoxic and selenium-rich sedimentary event. The authors think that the North China Craton and the Yangtze Craton were possibly in different tectonic locations of the same continental block during the Proterozoic.©2023 China Geology Editorial Office.     

Paleoproterozoic positive δ13Ccarb excursion in the northeastern Sino-Korean craton: Evidence of the Lomagundi Event

The 2.33–2.06 Ga positive δ¹³C_carb excursion, associated with environmental change and the breakup of the Kenorland or Superia supercontinent, is called the Lomagundi or Jatulian Event or Great Oxidation Event, and has been reported in many Early Precambrian cratons, but not yet in the Sino-Korean craton. The Guanmenshan Formation of the Liaohe Group occurs in the northeastern part of the Sino-Korean craton. δ¹³C_carb and δ¹⁸O values in 42 samples from this formation range from 3.5–5.9‰ (V-PDB), and 15.4–24.8‰ (V-SMOW), respectively, showing a clear positive δ¹³C_carb excursion that characterizes the Lomagundi Event. Thirty-five of the 42 samples with less hydrothermal alteration have higher δ¹³C_carb and δ¹⁸O_carb values than the other 7 samples obviously affected by fluid flow, confirming that it was fluid flow that reduced the δ¹³C_carb and δ¹⁸O_carb values. This positive δ¹³C_carb excursion places deposition of the Guanmenshan Formation within the age range of 2.33–2.06 Ga.     

Global perturbation of the marine Ca isotopic composition in the aftermath of the Marinoan global glaciation

Ca isotopic compositions of Marinoan post-glacial carbonate successions in Brazil and NW Canada were measured. Both basal dolostones display δ^44/40Ca values between 1 and 0.7‰, overlying limestones show a negative Ca isotope excursion to values around 0.1‰, and δ^44/40Ca values rapidly increase up-section to near 2.0‰. In the Brazilian successions, those high δ^44/40Ca values rapidly decrease and stabilize to values between 0.6 and 0.9‰. These Ca isotope secular variation trends are unlike those of Sturtian post-glacial carbonate successions, but similar to those of Marinoan post-glacial carbonate successions in Namibia, suggesting that the perturbation of the marine Ca cycle was global. This recommends Ca isotope stratigraphy as a tool to correlate Neoproterozoic post-glacial carbonate successions worldwide.     

Trace sulfate in mid-Proterozoic carbonates and the sulfur isotope record of biospheric evolution

Concentrations of oceanic and atmospheric oxygen have varied over geologic time as a function of sulfur and carbon cycling at or near the Earth’s surface. This balance is expressed in the sulfur isotope composition of seawater sulfate. Given the near absence of gypsum in pre-Phanerozoic sediments, trace amounts of carbonate-associated sulfate (CAS) within limestones or dolostones provide the best available constraints on the isotopic composition of sulfate in Precambrian seawater. Although absolute CAS concentrations, which range from those below detection to ∼120 ppm sulfate in this study, may be compromised by diagenesis, the sulfur isotope compositions can be buffered sufficiently to retain primary values.Stratigraphically controlled δ³⁴S measurements for CAS from three mid-Proterozoic carbonate successions (∼1.2 Ga Mescal Limestone, Apache Group, Arizona, USA; ∼1.45-1.47 Ga Helena and Newland formations, Belt Supergroup, Montana, USA; and ∼1.65 Ga Paradise Creek Formation, McNamara Group, NW Queensland, Australia) show large isotopic variability (+9.1‰ to +18.9‰, −1.1‰ to +27.3‰, and +14.1‰ to +37.3‰, respectively) over stratigraphic intervals of ∼50 to 450 m. This rapid variability, ranging from scattered to highly systematic, and overall low CAS abundances can be linked to sulfate concentrations in the mid-Proterozoic ocean that were substantially lower than those of the Phanerozoic but higher than values inferred for the Archean. Results from the Belt Supergroup specifically corroborate previous arguments for seawater contributions to the basin. Limited sulfate availability that tracks the oxygenation history of the early atmosphere is also consistent with the possibility of extensive deep-ocean sulfate reduction, the scarcity of bedded gypsum, and the stratigraphic δ³⁴S trends and ³⁴S enrichments commonly observed for iron sulfides of mid-Proterozoic age.     

Integrated chemostratigraphy and biostratigraphy of the Windermere Supergroup, northwestern Canada: implications for Neoproterozoic correlations and the early evolution of animals

The thick, richly fossiliferous succession of the upper Windermere Supergroup, Mackenzie Mountains, northwestern Canada, provides a test of integrated biostratigraphic and chemostratigraphic frameworks in terminal Proterozoic correlation. The C- and Sr-isotopic abundances of lower Keele Formation carbonates approximate those for other pre-Varanger samples, confirming that the simple disc-like fossils of the underlying Twitya Formation predate all known diverse Ediacaran faunas. "Tepee" and Sheepbed carbonates record strong post-glacial isotopic excursions; in contrast, delta13C values for Gametrail through Risky carbonates vary only within the narrow range of about +l% to +2%. A second negative excursion occurs in Ingta Formation carbonates that immediately underlie the paleontologically determined Precambrian-Cambrian boundary. The upper Windermere profile as a whole compares closely with curves determined for other terminal Proterozoic successions. The lowermost diverse Ediacaran assemblages in the Sheepbed Formation correlate chemostratigraphically with the oldest fauna in Namibia, but the two assemblages differ in taxonomic composition. Blueflower assemblages correlate both chemostratigraphically and taxonomically with faunas from Australia, China, Siberia, and elsewhere. Increasing data support the hypothesis that paleontological and geochemical data together provide a reliable means of correlating terminal Proterozoic sedimentary rocks throughout the world.     

A Paleoproterozoic drowned carbonate platform on the southeastern margin of the Wyoming Craton: a record of the Kenorland breakup

The Nash Fork Formation in the upper part of the early Paleoproterozoic Snowy Pass Supergroup, Medicine Bow Mountains of Wyoming, was deposited on a mature passive margin along the southern flank of the Wyoming Craton and straddles the end of the ca. 2.2–2.1 Ga carbon isotope excursion. Two drowning events marked by black shales subdivide the carbonate platform into three parts. The lower Nash Fork Formation consists of outer shelf to supratidal deposits represented by massive and stromatolitic dolomites, heterolithic siliciclastics-carbonates, large silicified domal digitate stromatolites, nodular dolomites and stromatolitic dolomites. Molds after evaporite crystals are pervasive in the heterolithic siliciclastics-carbonates. Large silicified domal digitate stromatolites formed biostromes and bioherms following flooding events. The middle Nash Fork Formation comprises two intervals of black shale separated by inner shelf heterolithic siliciclastics-nodular carbonates. Black shales are organic- and pyrite-rich, contain turbidites and developed in response to drowning of the platform. Overlying massive dolomite of the upper Nash Fork Formation was deposited in an unprotected intertidal setting and displays an upward-shallowing trend terminated by a prominent karstic surface in the middle of the unit. The Nash Fork Formation is open-marine with no evidence for restricted circulation on the carbonate platform. The two drowning events on the carbonate platform are likely related to dissection of the mature passive margin associated with the breakup of Kenorland. The younger drowning event is associated with the end of the carbon isotope excursion. The main building elements of the lower and middle Nash Fork carbonate platform are dolomitic mudstones and stromatolites. Macroscopic seafloor precipitates are volumetrically negligible with the exception of tufa deposits and domes in the massive and stromatolitic dolomites and, possibly, digitate stromatolites within domal digitate stromatolites. The upper Nash Fork Formation comprises dolomitic mudstones, relatively rare stromatolites and inorganic precipitates that are more common than in the underlying carbonates. Styles of carbonate deposition on this early Paleoproterozoic platform differ from those documented on late Archean carbonate platforms; there are fewer macroscopic seafloor precipitates and more dolomitic mudstones. This pattern is considered to be related to a rise of the atmospheric oxygen level that led to a decrease in bicarbonate saturation in the ocean.     

U-Pb provenance fingerprints of metavolcanic-sedimentary successions of the Mineiro belt: Proxies for the continuity of plate tectonics through the Paleoproterozoic

We document new U-Pb detrital zircon LA-MC-ICP-MS data for seven metavolcanic-sedimentary successions and metasedimentary sequences and reassess additional dates of five siliciclastic samples toward their tectonic significance in the context of the Mineiro belt, Southern São Francisco Craton. This belt represents a crustal segment of the 2.47–2.00 Ga Minas Orogen, classically known by its Siderian and Rhyacian juvenile rocks with important implications in the Earth's geodynamics. The new and compiled detrital provenance constraints unravel the long-lived magmatic and sedimentary history of the studied basins, lasting ca. 230–220 Myr. The maximum depositional dates around 2.1 Ga reflect the renewed sediment budget with the subsequent metamorphic episode ca. 2.0 Ga. Most of the unmixed relative probability diagrams are consistent with sourcing from the Siderian and Rhyacian arcs of the Mineiro belt, determining a detrital provenance change in time and space for the precursor basins. Alternative potential sources could be the youngest rocks of the Mantiqueira and Juiz de Fora terranes that constitute the other segments of the Minas Orogen, given the age match. The overall detrital fingerprints determine the study basins resumed mainly in Rhyacian fore-arc and/or back-arc settings, i.e., akin to a subduction-related system that evolved to a collisional (foreland) environment. Few samples show fingerprints of primary extensional settings, determined by major Archean detrital populations sourced from areas outside the Mineiro belt beside the Paleoproterozoic detritus. The working model considers the collage between the Mineiro belt and the ancient foreland around 2.10 Ga and eventual interaction with other crustal segments of the Minas Orogen, generating the ca. 2.0 Ga metamorphism over the metasedimentary samples. The more complete isotopic repository in detrital and igneous zircon grains for the studied supracrustal successions and the associated rocks allows new insights into the Rhyacian–Orosirian dynamics of the Minas orogeny. In a broader perspective, the juvenile nature of the Mineiro belt reinforces the paradigm of uninterrupted continental growth during the Paleoproterozoic Earth.     

Re-Os and Mo isotope systematics of black shales from the Middle Proterozoic Velkerri and Wollogorang Formations, McArthur Basin, northern Australia

Joint application of the Mo isotope paleoredox proxy and Re-Os deposition-age geochronometer to euxinic black shales has potential for tracing the evolution of ocean redox chemistry over geological time. Here, we report new Re-Os and Mo isotope data for the Mesoproterozoic Velkerri Formation (Roper Group) and Paleoproterozoic Wollogorang Formation (Tawallah Group), McArthur Basin, northern Australia. New Re-Os ages of 1361 ± 21 Ma (2σ, n = 14, mean square of weighted deviates [MSWD] = 1.3, Model 1) and 1417 ± 29 Ma (2σ, n = 12, MSWD = 1.3, Model 1) constrain the depositional age of the Velkerri Formation and its contained biomarkers, as well as acritarchs and microfossils from the Roper Group. Black shales from the upper Velkerri Formation have high Mo abundances (105-119 ppm) and degree of pyritization [DOP] values (0.90-0.92) implying quantitative conversion of molybdate (MoO₄²⁻) to thiomolybdate (MoS₄²⁻) in overlying bottom waters. The average δ^97/95Mo (0.72 ± 0.10‰, 2σ, n = 6) of these shales is consistent with previous data, but represents a significantly more precise determination for global seawater δ^97/95Mo at 1.4 Ga. This value is lighter than present-day seawater by ∼0.85‰ and reflects expanded strongly euxinic deep ocean conditions ([H₂S]_aq > 11 μM) relative to oxic, suboxic, and weakly/intermittently euxinic ([H₂S]_aq < 11 μM) marine deposition in the 1.4 Ga oceans. Mass-balance modelling suggests Mo removal into strongly euxinic and oxic sediments may have comprised 30-70% and less than 15%, respectively, of the oceanic Mo sink at 1.4 Ga as opposed to 5% and 35% today, respectively.The Re-Os radioisotope system in organic-rich shales serves as a test for post-depositional alteration that could affect the usefulness of paleoredox tracers such as Mo stable isotopes. Re-Os isotope data for the Wollogorang Formation black shales are scattered and yield a highly imprecise date of 1359 ± 150 Ma (2σ, n = 21, MSWD = 85, Model 3). This age is younger than U-Pb zircon ages from interbedded tuffs that constrain the age of deposition at ca. 1730 Ma. In conjunction with previous petrological, geochemical, and paleomagnetic data, the Re-Os isotope data suggest hydrothermal fluid flow through the Wollogorang Formation, possibly associated with formation of the ca. 1640 Ma McArthur River Pb-Zn-Ag sedimentary exhalative deposit, resulted in post-depositional mobilization of Re and Os. Based on the degree of deviation of the Re-Os data from a 1730 Ma reference line, open-system behavior of Re and Os was greatest near the base of the black shale unit. Wollogorang Formation black shales are enriched in Mo (41-58 ppm), but are characterized by variable δ^97/95Mo (0.3-0.8‰) and DOP (0.57-0.92). The lightest δ^97/95Mo values occur near the base of the black shale unit. Based on the Re-Os systematics, hydrothermal fluids have probably overprinted the authigenic δ^97/95Mo signature in those shales. However, the heaviest δ^97/95Mo values in the Wollogorang Formation come from stratigraphically higher shales, and are similar to those observed for the Velkerri Formation, and thus may reflect seawater δ^97/95Mo at 1.73 Ga.     

Sulfur and carbon isotope records from 1700 to 800 Ma carbonates of the Jixian section, northern China: Implications for secular isotope variations in Proterozoic seawater and relationships to global supercontinental events

This study is a comprehensive, stable isotope survey of the marine carbonate-dominated, upper Paleo- to lower Neoproterozoic stratigraphy of Jixian County, China. Carbonate-associated sulfate (CAS) was extracted and measured for δ³⁴S_CAS using the same samples analyzed for δ¹³C_carbonate. This integrated proxy approach is a step towards a more comprehensive picture of secular variation in the composition of Proterozoic seawater. We specifically sampled marine carbonate intervals from the lower section of the Chuanlinggou Formation, Changcheng Group (ca. 1700 Ma) to the top of the Jingeryu Formation, Qingbaikou Group (ca. 800 Ma). δ¹³C_carbonate values are mostly negative in the upper Paleoproterozoic Changcheng Group, with an ascending trend from −3‰ to 0‰. We observed variation of approximately 0 ± 1‰ in the Mesoproterozoic Jixian Group, and positive values of +2 ± 2‰ characterize the lower Neoproterozoic Qingbaikou Group. Stratigraphic variations in δ³⁴S_CAS are more remarkable in their ranges and magnitudes, including conspicuously high values exceeding +30‰ in the three intervals at ca. 1700 Ma, 1300-1100 Ma, and 1000-900 Ma. In the Changcheng Group, δ³⁴S_CAS values are typically higher than +25‰, with only a few values of less than +15‰. In contrast, most of the data spanning from the Mesoproterozoic Tieling Formation of the Jixian Group to the lower Neoproterozoic Jingeryu Formation of the Qingbaikou Group are highly variable between +10‰ and +25‰, with some values exceeding +25‰.In the late Paleoproterozoic (1700-1600 Ma), a >10‰ decrease in δ³⁴S_CAS and ∼3‰ increase in δ¹³C_carbonate are coincident with, and likely related to, the breakup of Columbia, a supercontinent that predated Rodinia. Carbon and sulfur isotope data from the Mesoproterozoic, when global tectonic activity was comparatively weaker, fall mostly in the ranges of +15 ± 10‰ and 0 ± 1‰, respectively, but fluctuations of >20‰ for δ³⁴S_CAS and >3‰ for the δ¹³C_carbonate at ca. 1450-1400 Ma may reflect subduction and large-scale magmatic activity in island arcs marking the end of Columbia breakup. From the late Mesoproterozoic (ca. 1300-1100 Ma) to the early Neoproterozoic (ca. 800 Ma), the δ¹³C and δ³⁴S of seawater increased gradually with increasing variability. Most impressive areδ³⁴S_CAS values that exceed +30‰ in two intervals at ca. 1300-1100 Ma and ca. 1000-900 Ma, which may reflect the assembly and early breakup of Rodinia. Although gaps in the record remain, and studies of even higher resolution are warranted, our results suggest that changes in paleoceanographic conditions linked to global tectonics strongly influenced the biogeochemical cycles of C and S. Furthermore, periods of the Proterozoic previously noted for their isotopic invariability show clear isotopic expressions of this tectonic activity.     

Carbon,oxygen and strontium isotope geochemistry of Proterozoic carbonate rocks of the Vindhyan Basin,central India

Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ¹³C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ¹³C compositions. In the central Vindhyan section, the carbonates exhibit positive δ¹³C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ¹⁸O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ ¹⁸O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved ⁸⁷Sr/⁸⁶Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ¹³C values from Upper Vindhyan are characterized by lower ⁸⁷Sr/⁸⁶Sr values (0.7068±2) than those with negative δ¹³C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.     

Storm Event Beds in a Paleoproterozoic Rift Basin, Aravalli Supergroup, Rajasthan, India

Storm event beds in the Paleoproterozoic riftogenic sedimentary succession of Aravalli Supergroup are described from a 12.8 m-thick sandstone-mudstone interbedded unit in Zawar area, Rajasthan, India. The storm event beds include different primary structural assemblages indicating deposition from waning storm current. Sequential arrangement of beds with characteristic primary structural assemblages suggests deposition under a transgressive phase, and overall retrogradational evolution of the storm-succession provides evidence in favour of faster downsagging of the basin floor. The Pb-Zn sulphide ore bearing sedimentary succession of Zawar records repeated downsagging and exhumation of the basin floor in the frame of continental rift tectonics.     

Constraining atmospheric oxygen and seawater sulfate concentrations during Paleoproterozoic glaciation: In situ sulfur three-isotope microanalysis of pyrite from the Turee Creek Group, Western Australia

Previous efforts to constrain the timing of Paleoproterozoic atmospheric oxygenation have documented the disappearance of large, mass-independent sulfur isotope fractionation and an increase in mass-dependent sulfur isotope fractionation associated with multiple glaciations. At least one of these glacial events is preserved in diamictites of the ∼2.4 Ga Meteorite Bore Member of the Kungarra Formation, Turee Creek Group, Western Australia. Outcrop exposures of this unit show the transition from the Boolgeeda Iron Formation of the upper Hamersley Group into clastic, glaciomarine sedimentary rocks of the Turee Creek Group. Here we report in situ multiple sulfur isotope and elemental abundance measurements of sedimentary pyrite at high spatial resolution, as well as the occurrence of detrital pyrite in the Meteorite Bore Member. The 15.3‰ range of Δ³³S in one sample containing detrital pyrite (−3.6‰ to 11.7‰) is larger than previously reported worldwide, and there is evidence for mass-independent sulfur isotope fractionation in authigenic pyrite throughout the section (Δ³³S from −0.8‰ to 1.0‰). The 90‰ range in δ³⁴S observed (−45.5‰ to 46.4‰) strongly suggests microbial sulfate reduction under non-sulfate limiting conditions, indicating significant oxidative weathering of sulfides on the continents. Multiple generations of pyrite are preserved, typically represented by primary cores with low δ³⁴S (<−20‰) overgrown by euhedral rims with higher δ³⁴S (4-7‰) and enrichments in As, Ni, and Co. The preservation of extremely sharp sulfur isotope gradients (30‰/<4 μm) implies limited sulfur diffusion and provides time and temperature constraints on the metamorphic history of the Meteorite Bore Member. Together, these results suggest that the Meteorite Bore Member was deposited during the final stages of the “Great Oxidation Event,” when pO₂ first became sufficiently high to permit pervasive oxidative weathering of continental sulfides, yet remained low enough to permit the production and preservation of mass-independent sulfur isotope fractionation.     

Age constraints on the Palaeoproterozoic Lomagundi–Jatuli Event in Zimbabwe: Zircon geochronology of the Magondi Supergroup

The ca. 2.2–2.1 Ga Magondi Supergroup on the Zimbabwe Craton in Southern Africa is mainly composed of sedimentary rocks deposited in a rift basin/passive continental margin, which record a unique episode in carbon isotope perturbation called the Lomagundi–Jatuli Event (LJE). This study reports new U–Pb ages of detrital zircons from the Deweras and Lomagundi groups of the Magondi Supergroup, and of igneous zircons from underlying granitoids, to constrain the timing of the LJE and to identify the provenance of the Magondi Supergroup. Most analysed detrital zircon grains range in ages between ca. 2.9 and 2.6 Ga. Three ca. 2.3–2.2 Ga detrital zircons from sandstone of the Deweras Group, with the youngest ²⁰⁷Pb‐²⁰⁶Pb age of 2,216 ± 22 Ma, indicate the onset of LJE in the Zimbabwe Craton was almost simultaneous to that in Fennoscandia and the Superior Craton, supporting the global synchronicity of the LJE.