Lateral variations in the lithology and organic chemistry of a black shale sequence on the Mesoarchean seafloor affected by hydrothermal processes: The Dixon Island Formation of the coastal Pilbara Terrane,Western Australia

The Dixon Island Formation of the coastal Pilbara Terrane, Western Australia is a 3.2 Ga volcanic–sedimentary sequence influenced by syndepositional hydrothermal activity formed in an island‐arc setting. We documented lateral variations in stratigraphy, hydrothermal alteration, and biological activity recorded in the sedimentary rocks (over several kilometers), with the aim of identifying areas of biological activity and related small‐scale structures. The Dixon Island Formation comprises volcaniclastics, black chert, and iron‐rich chert within seven tectonic blocks. Based on detailed geological mapping, stratigraphic columns, carbon isotope composition, and organic carbon (C_org) content, we found lateral (>5 km) variations in stratigraphy and carbon isotope compositions in a black chert sequence above the Mesoarchean seafloor with hydrothermal activity. Two felsic tuff layers are used as stratigraphic marker beds within a black chert sequence, which was deposited on altered volcanic rocks. The black chert sequence in each tectonic block is 10–20 m thick. Thickness variations reflect topographical undulations in the paleo‐ocean floor due to faulting. Early‐stage normal faults indicate extensional conditions after hydrothermal activity. Black chert beds in the topographically subsided area contain higher C_org contents (about 0.4 wt%) than in areas around the depression (<0.1 wt%). Carbon isotope compositions for the black chert vary from ?40 to ?25‰, which are similar to values obtained for a black chert vein within the komatiite–rhyolite tuff sequence (underlying the black chert sequence). Those for other rock types in the Dixon Island Formation are ?33 to ?15‰. Results indicate that deformation occurred soon after the final stages of hydrothermal activity. After this early‐stage deformation, organic‐rich sediments were deposited over an area several kilometers across. The organic‐rich sediments indicate stagnant anoxic conditions that resulted in the deposition of siliceous and organic matter from hydrothermal vein systems. When hydrothermal activity terminated, normal faulting occurred and organic matter was deposited from the sea surface and silica from the seafloor.     

Organic carbon isotope gradient and ocean stratification across the late Ediacaran-Early Cambrian Yangtze Platform

Organic carbon isotope(δ13Corg) data from two well-preserved sections across a shallow-to-deep water transect of the late Ediacaran-Early Cambrian Yangtze Platform in South China show significant temporal and spatial variations. In the shallow-water Jiulongwan-Jijiapo section, δ13Corg values of the late Ediacaran Dengying Formation range from -29‰ to -24‰. In the deep-water Longbizui section, δ13Corg values from time-equivalent strata of the Dengying Formation are mostly between –35‰ and -32‰. These new data, in combination with δ13Corg data reported from other sections in South China, reveal a 6‰–8‰ shallow-to-deep water δ13Corg gradient. High δ13Corg values(-30‰) occur mostly in shallow-water carbonate rocks, whereas low δ13Corg values(-32‰) dominate the deep-water black shale and chert. The large temporal and spatial δ13Corg variations imply limited buffering effect from a large dissolved organic carbon(DOC) reservoir that was inferred to have existed in Ediacaran-Early Cambrian oceans. Instead, δ13Corg variations between platform and basin sections are more likely caused by differential microbial biomass contribution to total organic matter. High δ13Corg values(-30‰) documented from shallow-water carbonates are within the range of typical Phanerozoic δ13Corg data and may record the isotope signature of organic matter from primary(photosynthetic) production. In contrast, low δ13Corg values(-32‰) from deep-water sections may have resulted from higher chemoautotrophic or methanotrophic biomass contribution to bulk organic matter in anoxic environments. The δ13Corg data provide indirect evidence for ocean stratification and episodic chemocline fluctuations in the Ediacaran-Early Cambrian Yangtze Platform.     

Timing and development of sedimentation of the Cleaverville Formation and a post‐accretion pull‐apart system in the Cleaverville area,coastal Pilbara Terrane,Pilbara, Western Australia

In the Cleaverville area of Western Australia, the Regal, Dixon Island, and Cleaverville Formations preserve a Mesoarchean lower‐greenschist‐facies volcano‐sedimentary succession in the coastal Pilbara Terrane. These formations are distributed in a rhomboidal‐shaped area and are unconformably overlain by two narrowly distributed shallow‐marine sedimentary sequences: the Sixty‐Six Hill and Forty‐Four Hill Members of the Lizard Hills Formation. The former member is preserved within the core of the Cleaverville Syncline and the latter formed along the northeast‐trending Eighty‐Seven Fault. Based on the metamorphic grade and structures, two deformation events are recognized: D₁ resulted in folding caused by a collisional event, and D₂ resulted in regional sinistral strike‐slip deformation. A previous study reported that the Cleaverville Formation was deposited at 3020 Ma, after the Prinsep Orogeny (3070–3050 Ma). Our SHRIMP U–Pb zircon ages show that: (i) graded volcaniclastic–felsic tuff within the black shale sequence below the banded iron formation in the Cleaverville Formation yields an age of (3 114 ±14) Ma; (ii) the youngest zircons in sandstones of the Sixty‐Six Hill Member, which unconformably overlies pillow basalt of the Regal Formation, yield ages of 3090–3060 Ma; and (iii) zircons in sandstones of the Forty‐Four Hill Member show two age peaks at 3270 Ma and 3020 Ma. In this way, the Cleaverville Formation was deposited at 3114–3060 Ma and was deformed at 3070–3050 Ma (D₁). Depositional age of the Cleaverville Formation is at least 40–90 Myr older than that proposed in previous studies and pre‐dates the Prinsep Orogeny (3070–3050 Ma). After 3020 Ma, D₂ resulted in the formation of a regional strike‐slip pull‐apart basin in the Cleaverville area. The lower‐greenschist‐facies volcano‐sedimentary rocks are distributed only within this basin structure. This strike‐slip deformation was synchronous with crustal‐scale sinistral shear deformation (3000–2930 Ma) in the Pilbara region.     

Late Cretaceous paleoenvironment and lake level fluctuation in the Songliao Basin,northeastern China

Study of Late Cretaceous lacustrine sedimentary strata in the eastern Songliao Basin, China revealed that the paleoclimate was relatively arid and hot during sedimentation of the upper Santonian of the Yaojia Formation, but became relatively humid and warm during deposition of the lower Campanian Nenjiang Formation. The upper Yaojia Formation was deposited in a freshwater lake environment, while the lower Nenjiang Formation was deposited in a slightly brackish to brackish environment. The average total organic carbon content in the upper Yaojia Formation is 0.15%, while the hydrogen index is 36 mg_HC/g_TOC, implying poor source rock for oil generation and the organic matter comprised of a mixture of woody and herbaceous organic matter. In contrast, the hydrogen index of oil shale and black shale of the lower Nenjiang Formation is 619 mg_HC/g_TOC, and total organic carbon content on average is 3.37%, indicating a mixed algae and herbaceous source of kerogen and an increase in aquatic bioproductivity. The black shale and oil shale have low Pristane/Phytane and C₂₉ 5α,14α,17α(H) ? stigmastane 20R/(20R + 20S) ratios, with maximum concentration of n‐alkanes at n‐C₂₃, implying an anoxic depositional environment with algae, bacteria and higher plants providing most of the organic matter. Relatively abundant gammacerane and a higher Sr/Ba ratio in the oil shales suggest the presence of brackish water and development of salinity stratification in the lake. During sedimentation of the upper Yaojia through the lower Nenjiang Formations, the level of Songliao lake increased and a deep‐lake environment was formed with bottom waters being oxygen depleted. Concomitantly, as the lake deepened bottom conditions were changing from oxic to anoxic, and the input of organic matter changed from predominantly higher plants to a mixture of bacteria, algae and higher plants providing favorable conditions for oil source rock accumulation.     

Trace elements and stable isotopic geochemistry of an Early Cambrian chert-phosphorite unit from the lower Yurtus Formation of the Sugetbrak section in the Tarim Basin

A chert-phosphorite unit from the Sugetbrak section in the Tarim Basin was analyzed for rare earth elements (Ce, Eu), redox sensitive proxies, and carbon isotopic compositions (δ¹³C_carb and δ ¹³C_org) in the lower Yurtus Formation of the Early Cambrian period. Redox sensitive element ratios (Th/U, V/Cr, Ni/Co, and V/Sc) were employed to determine the palaeoenvironmental conditions during this period. The ratios indicated that the depositional environment of the chert-phosphorite-black shale unit ranged from suboxic to anoxic. Negative Ce and positive Eu anomalies in the chert-phosphorite assemblages of the studied Yurtus Formation indicated the existence of a redox-stratified ocean, similar to that of South China. Overturn or upward expansion of the deep water-mass probably reached the shallow marine zone after the formation of the Yurtus phosphorites. The characteristics of the negative Ce anomaly may be due to phosphoritic inheritance from the Ce-depleted signature of the overlying water column. Subsequent hydrothermal inputs and reduced detrital supplies of the deep water caused by the upwelling affected certain redox sensitive elements in the sedimentary basin. δ ¹³C_carb and δ¹³C_org negative excursions in the Yurtus chert-phosphorite unit may be related to a transgression phase when episodic basinal upwelling moved ¹²C- and P-rich waters from the pelagic basin floor to the continental shelf. Although carbon isotopic compositions in the Yurtus chert-phosphorite assemblages may have suffered from diagenetic alteration, they can be used to probe diagenetic conditions. Multi-proxy geochemical studies indicated that the δ ¹³C_carb values of the Yurtus chert-phosphorite assemblages might be considered reflections of a predominantly suboxic environment that was subsequently affected by hydrothermal inputs due to the upwelling.     

Rhuddanian to Aeronian (Llandovery,early Silurian) carbon isotope stratigraphy throughout carbonate sequences in the upper Yangtze region,South China block

The Xiangshuyuan Formation (middle Rhuddanian to middle Aeronian stages of the Llandovery Series, lower Silurian) records a shelly fauna representing recovery after the end-Ordovician mass extinction in a well-oxygenated shallow carbonate platform of the Upper Yangtze region, South China Block. Carbon isotope stratigraphy is documented from limestone sequences of the formation at the Qiankou section, northeast Guizhou. The early Aeronian carbon isotope excursion (EACIE, with an amplitude of about 2 ‰ and peak value of 2.44 ‰) is identified in the middle and upper parts of the formation (Ozarkodina obesa conodont Biozone). The EACIE recorded herein correlates well with those in Baltica, Canada, and the United States; together with its records from organic material (δ¹³C_org) the data verify that the EACIE is a global event. The beginning of the EACIE can be used as a chemostratigraphic marker defining the Rhuddanian/Aeronian boundary in strata that lack high-resolution biostratigraphic constraints.     

Magnetostratigraphy of the late Tertiary Verde Formation,central Arizona

Paleomagnetic polarity data were obtained from nine sections of the Verde Formation, a late Tertiary carbonate-bearing lacustrine unit in central Arizona. This study tested the applicability of magnetostratigraphy as a geochronologic technique in a restricted terrestrial sedimentary basin, and its objective was to better define the age of the Verde Formation.Intensities of natural remanent magnetism (NRM) ranged from <10^?7 to >10^?4 gauss. Although secondary components of viscous magnetization commonly were observed, alternating field demagnetization was successful in revealing the polarity of the primary NRM at almost all sites. Thermomagnetic analysis, partial thermal demagnetization of NRM, and polished section analysis together indicate that the primary NRM is a depositional remanence carried by detrital magnetite. Intrabasin stratigraphic correlation of the sections, together with K-Ar ages on interbedded and underlying volcanic rocks has allowed construction of a composite magnetostratigraphic column for the Verde Formation that is correlated with the late Cenozoic polarity time scale. The correlation indicates nearly continuous sedimentation in the Verde basin from ～7.5 to ～2.5 m.y. ago.     

Upper Eocene travertine-lacustrine carbonate in the Jianchuan basin,southeastern Tibetan Plateau: Reappraisal of its origin and implication for the monsoon climate

The Asian monsoon is one of the largest climatic systems in the world, but age of its onset has been estimated differently ranging from the late Eocene to the Quaternary. We investigated the sedimentology and stable isotopic compositions of the upper Eocene Jiuziyan Formation, a terrestrial limestone unit in the Jianchuan basin, Yunnan Province in China. This limestone formation is restricted in several localities in the central part of the basin. Previously, this has been characterized as palustrine carbonate and the transition to the sublacustrine deposit of the overlying Shuanghe Formation was interpreted as the appearance of wetter climate during the late Eocene. Our observations of macro- and microfacies revealed sedimentary fabrics indicating rapid CaCO₃ precipitation, such as dendritic calcite and calcified reed stems, which are unlikely to develop in a simple lacustrine setting. High carbonate content (mostly >90 %) and restricted distribution of the Jiuziyan limestone indicate a depositional setting spatially limited and isolated from clastic influx. These findings, together with clearly higher δ¹³C values (−0.7 ‰ to +6.9 ‰) and lower δ¹⁸O values (−14.6 ‰ to −10.5 ‰) than those of the Shuanghe Formation, indicate that the limestone was mainly travertine, carbonate formed from endogenic spring water. The elevated δ¹³C resulted from a large amount of CO₂ degassing from spring water with high pCO₂. In addition, the occurrence of centimeter-scale lamination coupled with cyclic changes in δ¹³C and δ¹⁸O is almost identical with the modern annually-laminated travertine reported from Baishuitai in northern Yunnan Province, implying comparable amplitude of seasonal temperature and precipitation changes to the record of the modern travertine at Baishuitai. Our results do not contradict the previous interpretation of late Eocene wetting and additionally suggest the existence of the late Eocene monsoon climate in the Jianchuan basin.     

Fourth‐ to third‐order cycles in the Hakobuchi Formation: Shallow‐marine Campanian final deposition of the Yezo Group,Nakagawa area,northern Hokkaido,Japan

The Yezo Group has a wide longitudinal distribution across Hokkaido, northern Japan. It represents a Cretaceous (Early Aptian–Late Maastrichtian) and Late Paleocene forearc basin‐fill along the eastern margin of the paleo‐Asian continent. In the Nakagawa area of northern Hokkaido, the uppermost part of the Yezo Group consists of the Hakobuchi Formation. Along the western margin of the Yezo basin, 24 sedimentary facies (F) represent 6 facies associations (FA), suggesting prevailing storm‐dominated inner shelf to shoreface environments, subordinately associated with shoreface sand ridges, outer shelf, estuary and fluvial environments. The stacking patterns, thickness and facies trends of these associations allow the discrimination of six depositional sequences (DS). Inoceramids Sphenoceramus schmidti and Inoceramus balticus, and the ammonite Metaplacenticeras subtilistriatum, provide late Early to Late Campanian age constraints to this approximately 370‐m thick final stage of deposition and uplift of the Yezo forearc basin. Six shallow‐marine to subordinately non‐marine sandstone‐dominated depositional sequences include four 10 to 110‐m thick upward‐coarsening regressive successions (FS1), occasionally associated with thin, less than 10‐m thick, upward‐fining transgressive successions (FS2). The lower DS1–3, middle DS4–5 and upper DS6 represent three depositional sequential sets (DSS1–3). These eastward prograding and westward retrograding recurring shallow‐marine depositional systems may reflect third‐ and fourth‐order relative sealevel changes, in terms of sequence stratigraphy.     

Sulfur isotope ratios of Icelandic lava incrustations and volcanic gases

Sulfur isotope ratios were measured in eight lava incrustations and three volcanic gas samples and their corresponding lava flows. The lava incrustations of sulfate composition are from five recent eruptions and occur as thenardite or as aphtitalite-thenardite mixtures, with abundant trace elements. The incrustations show small sulfur isotope fractionation of 1–2‰ compared with corresponding lavas and the volcanic gas samples. The sulfate incrustations are formed through oxidation of SO₂ from the emitted volcanic gas and subsequent reaction with metal halides. The volcanic gas samples show a distribution of decreasing δ³⁴S through time from +3.4 to −1.8‰; sulfate was preferentially degassed compared to sulfide. The data indicate that sulfate incrustations serve as a late-stage volcanic gas sample with respect to sulfur isotopes.     

Comprehensive constraint on the tectono-sedimentary setting of Late Paleozoic turbidites of the Kamuste area, eastern Junggar, Xinjiang

Petrography and geochemistry, combined with sedimentation analyses allow for a thorough evaluation of the tectono-sedimentary setting of late Paleozoic turbidites of the Kamuste area, eastern Junggar. Sandstones of the Alabiye¹⁾ Formation are composed mostly of volcanic and sedimentary detritus with lesser amounts of plagioclase and quartz. They were derived from an undissected magmatic-arc provenance. The geochemistry of sandstone-mudrock suites indicates a fesic-intermediate igneous provenance, and constrains the Alabiye Formation to have derived from a differentiated oceanic-continental margin island-arc tectonic setting. Likewise, geochemistry and sandstone petrography of the Kamuste Formation reflect a mixed provenance signature dominated by magmatic arc, basement uplift, and subduction-complex sources of a differentiated continental-island arc. Sedimentation analysis indicates that the Alabiye and Kamuste formations are two sets of turbidite sequences deposited on a submarine slope and a submarine fan and basin plain respectively. In conclusion, submarine slope turbidite deposition of the Alabiye Formation records the main sedimentary response to the development of early Devonian back-arc basins of the northern Junggar tectonic belt. Submarine fan and basin plain turbidite and background hemipelagic deposition of the Kamuste Formation record the main sedimentary response to the late Early Carboniferous development of an inter-arc relict ocean basin of the eastern Junggar composite terrane.     

Sedimentary filling and sequence structure dominated by T-R cycles of the Nenjiang Formation in the Songliao Basin

The Nenjiang Formation in the Songliao Basin is a symmetrical sequence of progradation-retrogradation,and is formed in the transgression cycle and regression cycle(T-R cycles)of the base level of deposition.We analyzed the drilling,well logging,core data,and seismic profiles of basin level,and by using the sequence stratigraphy,identified one secondary sequence boundary,two third-order sequence boundaries,and eight fourth-order sequence boundaries in the Nenjiang Formation.These eleven sequence boundaries can be divided into structural unconformity,depositional unconformity,flooding surface,and forced regression surface.Therefore the Nenjiang Formation can be subdivided into one secondary sequence,three third-order sequences,and ten fourth-order sequences.We have restored the sedimentary filling evolution within the stratigraphic framework of fourth-order sequences in the Nenjiang Formation.The sedimentary period of the first member of the Nenjiang Formation was corresponded to the global transgression period,which is also the development period of transgression cycle(T cycle),when the lake basin had the largest scope and deepest sedimentary water,the SB07(the maximum flooding surface)was formed on the top of strata during this period;covering above the SB07,there developed a set of condensation layer-oil shale,which is distributed in the whole basin and is the important source bed and regional cover.Therefore,a retrogradation sequence was formed in the T cycle of the first member of the Nenjiang Formation,characterized by the retrograding delta at a low angle.The delta has a giant front,a small plain,and many underwater distributary channels.Meanwhile,large gravity flow channels and sublacustrine fans are developed in the front of the delta.During the depositional period of the second member of the Nenjiang Formation,the R cycle began to develop due to the compression of the pacific tectonic domain;the source direction rotated 90°along with the eastern uplifting of the basin,and formed a series of east-west prograded and forced retrogradations.The prograding delta at high angel was developed in the interior of the sequence;the delta had a small front,a giant plain,and fewer underwater distributary channels,with the collapse at the foreslope,forming a series of slump fans.The slump fans can be divided into three types:discrete type,superimposed type,and fluid type.We built a whole"triad model"of the slump fan.Pointed out that the sequence of forced retrogradation formed by R cycle is a good structural mark of basin optimization,and rejected the viewpoint of"transgression"in the Nenjiang Formation of the Songliao Basin.     

Fractionation of sulfur isotopes by sediment adsorption of sulfate

Adsorption studies with sediment from the Bay of Quinte (Lake Ontario) indicate that the adsorption isotherm for sulfate concentration greater than 20 mg/l can be described by a Langmuir-type equation. The accompanying changes in δ³⁴S of the solutions range from +0.9 to +6.0‰ indicating enrichment of³²S in the sediments. The corresponding isotopic fractionation between the adsorbed sulfate and the sulfate remaining in solution ranges from ?10 to ?24‰, the larger fractionations being associated with low sulfate concentrations. The adsorbed sulfate is shown to significantly afftect the isotopic composition of the sediment in contact with the sulfate-bearing solution. The desorption of adsorbed sulfate is considered a possible mechanism for enriching natural freshwaters with³²S.     

Utilisation of different carbon sources in a shallow estuary identified through stable isotope techniques

Organic carbon in estuarine sediments can have many different sources. Terrestrial, riverine, estuarine and marine C pools may all contribute to and influence the organic C (C_org) inventory of the estuarine sediments and the differing stable isotope signatures of the sources are reflected in the sediment's overall ¹³C content. Ecological interpretations of sedimentary isotope data may, however, be limited by the fact the total C_org inventory of a sediment may not be an accurate representation of the fraction that is labile and being actively turned over by the sedimentary community. To gain a better understanding of sedimentary C_org dynamics in estuaries and the relationship between the sedimentary C pool and the C_org undergoing mineralisation, we studied three components of an estuarine system: (1) the sedimentary C_org inventory on a transect from the mouth to the upper end of the estuary, (2) temporal changes of sedimentary C_org at one station throughout a year, and (3) the δ¹³C of respired CO₂ compared to the δ¹³C of available source material and sedimentary C_org in a novel application of methods developed for soil science. Our experiments demonstrated that material of marine origin dominated the studied estuary. At the time-series station, material of marine origin dominated the sedimentary C_org throughout the 1-yr study period. δ¹³C values of CO₂ released from the sediment differed significantly from the sedimentary C_org inventory at all study sites, but also clearly reflected differences between the main sections of the estuary. These results suggest that δ¹³C measurements of respired CO₂ are promising as a tool to advance our understanding of C cycling in estuaries, and highlight that the sedimentary C_org pool alone may not be a satisfactory indicator of OM utilisation in estuarine sediments.     

High‐resolution lithostratigraphy and organic carbon isotope stratigraphy of the Lower Triassic pelagic sequence in central Japan

After the severest mass extinction event in the Phanerozoic, biotic recovery from the extinction at the Permian–Triassic boundary required approximately 5 my, which covers the entire Early Triassic. It is important to obtain information on the superocean Panthalassa, which occupied most of the world ocean, to explore paleoenvironmental changes during the Early Triassic at the global scale. In order to establish the continuous lithostratigraphy of pelagic sediments in Panthalassa during the Early Triassic, high‐resolution reconstruction of the Lower Triassic pelagic sequence in Japan was conducted for the first time based on detailed field mapping and lithostratigraphic correlation in the Inuyama area, central Japan. The reconstructed Early Triassic sequence is approximately 9.5 m thick, consists of five rock types, and is divided into eight lithological units. For the reconstructed continuous sequence, measurement of carbon isotopic composition of sedimentary organic matter (δ¹³C_org) was carried out. Stratigraphic variation of the δ¹³C_org value shows large‐amplitude fluctuations between ?34.4 and ?21.0‰ throughout the sequence. In order to establish a higher resolution age model for the reconstructed Lower Triassic pelagic sequence, we correlated δ¹³C_org records in the Inuyama area with high‐resolution isotopic profiles of carbonate carbon (δ¹³C_carb) from shallow‐marine carbonate sequences in southern China based on the similarity in general variation patterns with age constraints by radiolarian and conodont biostratigraphy. The result provides a high‐resolution time scale for the pelagic sequence of Panthalassa during the Smithian and Spathian. The age model suggests a drastic increase in sedimentation rate during the late Smithian, which should have been caused by the increase in terrigenous input to this site.     

Multiple sulfur isotope chemostratigraphy across the Permian–Triassic boundary at Chaotian,China: Implications for a shoaling model of toxic deep-waters

Previous studies on multiple sulfur isotopes (³²S, ³³S, and ³⁴S) in sedimentary pyrite at the end-Permian suggested a shoaling of anoxic/sulfidic deep-water contributing to the extinction. This scenario is based on an assumption that the sedimentary sulfur cycle was largely controlled by benthos activity, though a stratigraphic correlation between the sulfur records and ichnofabrics of the sediments at the end-Permian has not yet been examined. We report the multiple sulfur isotopic composition of pyrite in the Permian–Triassic boundary interval at Chaotian, South China. Our data can be generally explained by a mixing of sulfur in sulfide from two different sources: one produced via sulfate reduction in an open system with respect to sulfate and the other produced in a closed system. In particular, the former with the substantially low δ³⁴S (<−40 ‰) and high ∆³³S (up to +0.100 ‰) values was likely produced via water-mass sulfate reduction or via sulfate reduction in oxic sediments with common burrows. The frequent occurrence of small pyrite framboids (mostly <5 μm in diameter) in the Lopingian (Late Permian) Dalong Formation of deep-water facies supports the enhanced water-mass sulfate reduction in an anoxic deep-water mass. The negative ∆³³S values are observed only in the oxic limestones, and no substantial ∆³³S change is observed across the extinction horizon despite of the disappearance of bioturbation. Our results are apparently inconsistent with the previous shoaling model. We expand the model and infer that, when the deep-water was sulfidic and its shoaling rate was high, a substantial amount of hydrogen sulfide (H₂S) was supplied onto the shelf via the shoaling; that resulted in the positive ∆³³S value of the bulk sediments. The observed ∆³³S variation on a global scale suggests a substantial variation in H₂S concentration and/or in upwelling rate of shoaling deep-waters during the Permian–Triassic transition.     

Isotope shifts in the Late Permian of the Delaware Basin,Texas, precisely timed by varved sediments

Closely spaced samples (285 in number) of varved sediments from the Upper Permian in Delaware Basin, Texas, have been analyzed for δ¹³C_carb, δ¹³C_org, δ¹⁸O_carb, C_org, C_carb, and calcite/dolomite. δ¹³C records a dramatic rise from ?2.8 to +5.7‰ in only 4400 years, detected in three sections across the basin, extrapolating smoothly through a 600-year interruption by a local (west side of the basin) fresh-water inflow evidenced by low δ¹⁸O. This continuity and low C_org within the basin, both indicate that the excess net deposition of C_org, necessary to generate the rise in δ¹³C, took place in the ocean external to the Delaware Basin. Correlation with similar records from the Zechstein Basin suggest that the event was world-wide, although this poses obvious difficulties for the carbon cycle. The rate of rise of δ¹³C, and its sustained high level, must imply conversions of oxidized carbon to reduced carbon that are very large depending on which reservoirs were involved.     

The Whitsunday Volcanic Province, Central Queensland, Australia: lithological and stratigraphic investigations of a silicic-dominated large igneous province

Contrary to general belief, not all large igneous provinces (LIPs) are characterised by rocks of basaltic composition. Silicic-dominated LIPs, such as the Whitsunday Volcanic Province of NE Australia, are being increasingly recognised in the rock record. These silicic LIPs are consistent in being: (1) volumetrically dominated by ignimbrite; (2) active over prolonged periods (40–50 m.y.), based on available age data; and (3) spatially and temporally associated with plate break-up. This silicic-dominated LIP, related to the break-up of eastern continental Gondwana, is also significant for being the source of >1.4×10⁶ km³ of coeval volcanogenic sediment preserved in adjacent sedimentary basins of eastern Australia.The Whitsunday Volcanic Province is volumetrically dominated by medium- to high-grade, dacitic to rhyolitic lithic ignimbrites. Individual ignimbrite units are commonly between 10 and 100 m thick, and the ignimbrite-dominated sequences exceed 1 km in thickness. Coarse lithic lag breccias containing clasts up to 6 m diameter are associated with the ignimbrites in proximal sections. Pyroclastic surge and fallout deposits, subordinate basaltic to rhyolitic lavas, phreatomagmatic deposits, and locally significant thicknesses of coarse-grained volcanogenic conglomerate and sandstone are interbedded with the ignimbrites. The volcanic sequences are intruded by gabbro/dolerite to rhyolite dykes (up to 50 m in width), sills and comagmatic granite. Dyke orientations are primarily from NW to NNE.The volcanic sequences are characterised by the interstratification of proximal/near-vent lithofacies such as rhyolite domes and lavas, and basaltic agglomerate, with medial to distal facies of ignimbrite. The burial of these near-vent lithofacies by ignimbrites, coupled with the paucity of mass wastage products such as debris-flow deposits indicates a low-relief depositional environment. Furthermore, the volcanic succession records a temporal change in: (1) eruptive styles; (2) the nature of source vents; and (3) erupted compositions. An early explosive dacitic pyroclastic phase was succeeded by a later mixed pyroclastic-effusive phase producing an essentially bimodal suite of lavas and rhyolitic ignimbrite. From the nature and distribution of volcanic lithofacies, the volcanic sequences are interpreted to record the evolution of a multiple vent, low-relief volcanic region, dominated by several large caldera centres.     

Sand veins and MISS from the Mesoproterozoic black shale (ca. 1.7 Ga) in North China: Implication for methane degassing from microbial mats

The Mesoproterozoic Chuanlinggou Formation (ca. 1.7 Ga) consists mainly of dark-gray to black shales that are widespread in the North China Platform. Abundant centimeter-scale sand veins are present within the shale layers of this unit, particularly in the middle part. Sand veins display ptygmatic shapes, perpendicular or with a high angle to bedding planes. They penetrate the black shale layers but are often terminated by thin, lenticular sandstone beds, forming small-scale ‘tepee-like’ structures. On bedding planes, sand veins are expressed as small ridges with 1–3 mm positive relief. Lack of polygonal shapes and their occurrence in thinly laminated, relatively deep-water shales preclude an origin from sand-filled desiccation cracks. Instead, their close association with microbially induced sedimentary structures (MISS) such as micro-wrinkles and gas blisters, putative bacterial fossils (possibly coccoidal cyanobacteria) and framboidal pyrites, suggests that they were formed by degassing of methane from microbial mat decay. Methane gas disrupted overlying sedimentary layers, creating fractures open to seawater. Fine-grained quartz sands, which were transported into the depositional environment by strong winds, filled the fractures. Sand-filled fractures were shortened and folded during burial compaction, forming ptygmatic shapes. The presence of dispersed dolomite and siderite in these sand veins suggests authigenic carbonate precipitation from anaerobic oxidation of methane (AOM). Sand veins are intensely distributed within the Chuanlinggou Formation and are spatially widespread in the North China Platform. If their methane origin is confirmed, they may have important implications for the Mesoproterozoic paleoclimate. With anoxic oceans and low seawater sulfate concentration during the Mesoproterozoic, methane release from microbial mat decay and/or microbial methanogenesis during shallow burial may have been proportionally higher than that of the modern marine environments, with resultant increase in the relative importance of methane in maintaining the Mesoproterozoic greenhouse climate.     

Sulfur and carbon isotopic systematics of Guadalupian‐Lopingian (Permian) mid‐Panthalassa: δ34S and δ13C profiles in accreted paleo‐atoll carbonates in Japan

Immediately before the extinction of the end‐Guadalupian (Middle Permian; ca 260 Ma), a significant change to the global carbon cycle occurred in the superocean Panthalassa, as indicated by a prominent positive δ¹³C excursion called the Kamura event. However, the causes of this event and its connection to the major extinction of marine invertebrates remain unclear. To understand the mutual relationships between these changes, we analyzed the sulfur isotope ratio of the carbonate‐associated sulfate (CAS) and HCl‐insoluble residue, as well as the carbon isotope ratio of bulk organic matter, for the Middle‐Upper Permian carbonates of an accreted mid‐oceanic paleo‐atoll complex from Japan, where the Kamura event was first documented. We detected the following unique aspects of the stable carbon and sulfur isotope records. First, the extremely high δ¹³C values of carbonate (δ¹³C_carb) over +5 ‰ during the Capitanian (late Guadalupian) were associated with large isotopic differences between carbonate and organic matter (Δ¹³C = δ¹³C_carb ? δ¹³C_org). We infer that the Capitanian Kamura event reflected an unusually large amount of dissolved organic matter in the expanded oxygen minimum zone at mid‐depth. Second, the δ³⁴S values of CAS (δ³⁴S_CAS) were inversely correlated with the δ¹³C_carb values during the Capitanian to early Wuchiapingian (early Late Permian) interval. The Capitanian trend may have appeared under increased oceanic sulfate conditions, which were accelerated by intense volcanic outgassing. Bacterial sulfate reduction with increased sulfate concentrations in seawater may have stimulated the production of pyrite that may have incorporated iron in pre‐existing iron hydroxide/oxide. This stimulated phosphorus release, which enhanced organic matter production and resulted in high δ¹³C_carb. Low δ³⁴S_CAS values under high sulfate concentrations were maintained and the continuous supply of sulfate cannot by explained only by the volcanic eruption of the Emeishan Trap, which has been proposed as a cause of the extinction. The Wuchiapingian δ³⁴S_CAS–δ¹³C_carb correlation, likely related to low sulfate concentration, may have been caused by the removal of oceanic sulfate through the massive evaporite deposition.