Shallow Chemocline Research Articles

A shift in redox conditions near the Ediacaran/Cambrian transition and its possible influence on early animal evolution, Corumbá Group, Brazil

The Ediacaran–Cambrian transition witnessed some of the most important biological, tectonic, climatic and geochemical changes in Earth’s history. Of utmost importance for early animal evolution is the likely shift in redox conditions of bottom waters, which might have taken place in distinct pulses during the late Ediacaran and early Paleozoic. To track redox changes during this transition, we present new trace element, total organic carbon and both inorganic and organic carbon isotopes, and the first iron speciation data on the Tamengo and Guaicurus formations of the Corumbá Group in western Brazil, which record important paleobiological changes between 555 Ma to < 541 Ma. The stratigraphically older Tamengo Formation is composed mainly of limestone with interbedded marls and mudrocks, and bears fragments of upper Ediacaran biomineralized fossils such as Cloudina lucianoi and Corumbella werneri. The younger Guaicurus Formation represents a regional transgression of the shallow carbonate platform and is composed of a homogeneous fine-grained siliciclastic succession, bearing meiofaunal bilateral burrows. The new iron speciation data reveal predominantly anoxic and ferruginous (non-sulfidic) bottom water conditions during deposition of the Tamengo Formation, with FeHR/FeT around 0.8 and FePy/FeHR below 0.7. The transition from the Tamengo to the Guaicurus Formation is marked by a stratigraphically rapid drop in FeHR/FeT to below 0.2, recording a shift to likely oxic bottom waters, which persist upsection. Redox-sensitive element (RSE) concentrations are muted in both formations, but consistent with non-sulfidic bottom water conditions throughout. We interpret the collected data to reflect a transition between two distinct paleoenvironmental settings. The Tamengo Formation represents an environment with anoxic bottom waters, with fragments of biomineralized organisms that lived on shallower, probably mildly oxygenated surficial waters, and that were then transported down-slope. Similar to coeval successions (e.g., the Nama Group in Namibia), our data support the hypothesis that late Ediacaran biomineralized organisms lived in a thin oxygenated surface layer above a relatively shallow chemocline. The Guaicurus Formation, on the other hand, records the expansion of oxic conditions to deeper waters during a sea level rise. Although the relationship between global biogeochemical changes and the activities of early bioturbators remains complex, these results demonstrate an unequivocal synchronous relationship between oxygenation of the Corumbá basin and the local appearance of meiofaunal bioturbators.

The Shahejie Formation in the Dongpu Depression, Bohai Bay Basin, China: Geochemical investigation of the origin, deposition and preservation of organic matter in a saline lacustrine environment during the Middle Eocene

The Eocene Shahejie Formation in the Bohai Bay, Eastern China is known to contain important petroleum source rocks. Here, a new, large set of geochemical, petrographical and mineralogical data obtained on 41 samples from 9 wells within the North Dongpu Depression is presented in order to investigate organic matter precursor material, thermal maturity as well as paleoenvironment during deposition of the Es3U, Es3L, Es3M and Es4U members within the Eocene Shahejie Formation. These shales and marlstones from the four sub-members show low to moderate TOC contents (up to 5%) with highest values in the Es3U member; quartz content is at about 10% and carbonate content is variable, partly reaching more than 40%. A range of different maturity parameters was determined indicating early mature to peak oil mature stages, and maturity increase with burial depth. Throughout, alginite is the predominant maceral, whereas both vitrinite and inertinite are rare. Hydrogen index values are highly variable, ranging from about 100 to 700. Distinctly different biomarker assemblages indicate variable depositional environments and organic matter inputs between the four intervals. The Eocene Shahejie shales and marlstones in the study area were deposited under episodic photic zone anoxia as revealed by the presence of aryl isoprenoids. Bottom water conditions were anoxic during most of the time, except for Es3M, as indicated by several parameters, e.g. low pristane/phytane ratios. In north Dongpu Depression Es4U displays a fairly uniform biomarker composition, which indicates relatively stable hypersaline lake conditions with a shallow chemocline based on the high Gammacerane Index > 0.6 and abundant aryl isoprenoids. Water salinity changed during deposition of Es3L according to variable C24 tetracyclic terpanes related parameters and evaporite minerals content. The aquatic algal organisms, i.e. haptophyte algae, diatoms and bryophytes which are reflected by abundant nC37–39 alkanes, a variable sterane pattern and other biomarkers, were flourishing during Es3L. Additionally, specific PAHs, i.e. retene, cadalene, fluoranthene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene also have been identified in small concentration in Es3L, which may be attributed to limited terrigenous organic matter input. Es3M was deposited in a normal lacustrine environment under rather low salinity conditions with substantial input of organic matter derived from algae. During Es3U, saline lake conditions were re-established accompanied by input of both algal and microbial organic matter, especially cyanobacteria as deduced from MMAs and 2α-MeHs, methanogens as deduced from abnormally abundant phytane, PMI, squalane, and methanotrophs from 3β-MeHs.

Iron and manganese shuttle has no effect on sedimentary thallium and vanadium isotope signatures in Black Sea sediments

Thallium and V isotopes in organic-rich sediments have recently been explored for reconstructing marine oxygenation by tracking the burial of Mn oxides either locally or globally. The ‘Fe and Mn shuttle’ is a well known mechanism that can transport elements associated with Fe and Mn oxide phases formed under mildly oxidizing shallow water environments both laterally and vertically to euxinic (sulfidic water column) deep waters. The Fe and Mn shuttle has been demonstrated to strongly affect Fe and Mo isotope compositions of sediments accumulating beneath anoxic and euxinic settings. Similar to Mo, Tl and V are also enriched in oceanic ferromanganese crust and nodules, which impart the largest isotopic offsets from modern seawater for Tl and V. Thus, the mechanism of an Fe and Mn shuttle has the potential to, but currently unconstrained, affect Tl and V isotopic compositions (ε205Tl and δ51V) in organic-rich sediments in the modern and ancient records.We have used Black Sea sediments that are known to preserve enrichment and sedimentary isotope signatures for an Fe shuttle. This is due to an Fe transport from the more oxic margin to the deep euxinic basin and corresponding enrichment in the underlying sediments. These samples were used to test for a potential Fe and Mn shuttle effect on ε205Tl and δ51V in sediments deposited under oxic, suboxic, and euxinic water columns. Authigenic ε205Tl from all three depositional settings is indistinguishable (–2.7 ± 0.3, –2.4 ± 0.5, and –2.4 ± 0.3), which is within error of the Black Sea surface seawater (–2.2 ± 0.3). In contrast, oxic and suboxic sediment have similar δ51V values (–1.06 ± 0.33‰ and –1.04 ± 0.30‰), which are significantly more negative than euxinic sediments (–0.57 ± 0.06‰).All the sediments deposited under oxic, suboxic, and euxinic water columns in the Black Sea capture ε205Tl of the surface seawater because there is almost no permanent burial of Mn oxides in this basin. This finding is consistent with the indistinguishable ε205Tl between the surface seawater and the riverine input. Sedimentary δ51V appears to be controlled predominantly by the redox state of the depositional environments with little effect from an Fe or Mn shuttle. The lack of Fe and Mn shuttle effect on ε205Tl and δ51V in the Black Sea is likely due to the shallow (∼100 m) chemocline in the strongly, 2000-m deep redox-stratified water column of this basin and very slow deep-water renewal rate. Iron and Mn in oxides are not delivered to the sediments, instead, they are dissolved and captured in the water column as iron sulfide and reduced Mn mineral phases. Our results suggest that Fe and Mn shuttle transport mechanisms may not strongly affect Tl and V isotopes, at least in extreme cases of water column redox stratification. Further work is required to constrain the isotopic signals using other modern and, by inference, diverse ancient settings for additional shuttling mechanisms.

Depositional environment of Middle Triassic organic‐rich shales in the Ordos Basin, Northwest China

The Middle Triassic Tongchuan Formation in the Ordos Basin of northwestern China is a typical lacustrine deposit. A major component of this formation is thick layers of organic‐rich shales that are probably a potential hydrocarbon source and preserve the earliest known Mesozoic‐type lacustrine ecosystem. The exact depositional environment of the shales in the Tongchuan Formation, however, remains unknown. To address this question, we carried out high‐resolution carbon (δ13Corg) and sulphur (δ34Spy) isotope analysis as well as undertook total organic carbon (TOC)/pyrite contents and pyrite morphology investigation, and framboidal pyrite size measurements in shales of the Bawangzhuang section of the southern Ordos Basin. Remarkably high TOC (23 ± 9%) and pyrite (7 ± 3%) contents were obtained from the shales, which indicate a large amount of organic carbon and pyrite burial during shale deposition. Framboids are the dominant pyrite morphology in the pyrite crystals and show large and variable mean diameters (7.0 ± 1.7 μm to 14.3 ± 6.8 μm) across the section, indicating oxic–dysoxic bottom water during shale deposition. δ13Corg and δ34Spy revealed narrow and less variable values, ranging from −31.8‰ to −28.1‰, and −4.1‰ to 4.9‰, respectively. The δ13Corg values suggest balanced and consistent carbon cycles. Integrated with pyrite content and morphological patterns, consistent δ34Spy values probably demonstrate a relatively open environment for the formation of sedimentary pyrite, and thus a shallow chemocline that was quite close to the water‐to‐sediment interface during shale deposition. Overall, the organic‐rich shales of the Tongchuan Formation were probably deposited under oxic–dysoxic bottom‐water conditions. Shallow chemocline depth combined with moderately high sedimentation rate and high primary productivity may have played crucial roles in the deposition and formation of the organic‐rich shales in the Tongchuan Formation. The shallow chemocline also facilitates the fossil preservation in a lacustrine environment.

Biomarker stratigraphy in the Athel Trough of the South Oman Salt Basin at the Ediacaran-Cambrian Boundary.

The South Oman Salt Basin (SOSB) has been studied extensively for knowledge concerning the habitat of the enigmatic Ediacaran-Cambrian oils that are produced from that region. Geological, geochemical, geophysical, and geochronological investigations have all contributed to improved understanding of the range of late Neoproterozoic depositional environments recorded there. Of particular interest has been the deep Athel depocenter within the SOSB that features a silica-rich interval known as the Al Shomou Member or Athel Silicilyte and the co-eval A4 carbonate-evaporite sequence that straddles the Ediacaran-Cambrian boundary. The deep basin has been suggested to be anoxic and euxinic based on studies of sulfur isotopes, trace metal distributions and other proxies. Organic geochemistry has provided some clues concerning aspects of the depositional environments and microbial communities prevailing during this interval. However, ambiguities remain including a paucity of convincing molecular evidence for euxinia in the photic zone of the basin. Here, we present a comprehensive study of biomarker hydrocarbons, including steroids, triterpenoids, and carotenoids. Among the compounds detected is a distinctive array of aromatic carotenoids. Relatively low abundances of monoaromatic carotenoids, such as chlorobactane, okenane, and β-isorenieratane, suggest the possibility of transient photic zone euxinia with a shallow chemocline or, perhaps, exogenous inputs from microbial mats. However, it is the dominance of renieratane and renierapurpurane over isorenieratane in diaromatic carotenoids and their association with abundant C38 and C39 carotenoids that identifies cyanobacteria as major contributors to the inventory of carotenoids. Our results, based on multiple lines of molecular evidence and statistical analysis, also suggest that the Athel Silicilyte was biogeochemically distinct from the other units of the Ara Group. Overall, our study has important implications for understanding other late Neoproterozoic depositional environments.

Shallow water redox conditions of the mid-Proterozoic Muskwa Assemblage, British Columbia, Canada

The mid-Proterozoic was a time of apparent prolonged biological and geochemical stability, preceeding the environmental turmoil and rapid biological innovations that characterized the Neoproterozoic. Despite an upswing in work on the mid-Proterozoic over the past decade, basic aspects of the carbon cycle and Earth9s surface redox state during this time period remain poorly understood. To provide a new window into the mid-Proterozoic environmental evolution, we have investigated carbonates in the well-exposed Muskwa Assemblage located in NE British Columbia, Canada, for a combined stratigraphic and geochemical study. Rare Earth Elements and Yttrium (REE+Y) geochemistry was applied to carbonate rocks deposited over a marine paleoenvironmental depth gradient in order to characterize prevailing water column redox conditions. These data provide evidence for an extremely shallow chemocline with oxic surface waters being restricted to within storm-wave base, which is consistent with globally low oxygen in the ocean-atmosphere system. Furthermore, there is evidence for facies-dependent carbonate δ13C variability within the Muskwa Assemblage comparable in scale to typical stratigraphic variability recorded in carbonate strata of this age, highlighting the problems of using small carbon isotope excursions for chemostratigraphy.

Geochemical Characterization of Two Ferruginous Meromictic Lakes in the Upper Midwest, USA

AbstractTo elucidate the role of (bio)geochemical processes that fueled iron and carbon cycling in early Earth oceans, modern environments with similar geochemical conditions are needed. As the range of chemical, physical, and biological attributes of the Precambrian oceans must have varied in time and space, lakes of different compositions are useful to ask and answer different questions. Tropical Lake Matano (Indonesia), the largest known ferruginous lake, and Lake Pavin (France), a meromictic crater lake, are the two best studied Precambrian ocean analogs. Here we present seasonal geochemical data from two glacially formed temperate ferruginous lakes: Brownie Lake (MN) and Canyon Lake (MI) in the Upper Midwest, USA. The results of seasonal monitoring over multiple years indicate that (1) each lake is meromictic with a dense, anoxic monimolimnion, which is separated from the less dense, oxic mixolimnion by a sharp chemocline; (2) below this chemocline are ferruginous waters, with maximum dissolved iron concentrations &gt;1 mM; (3) meromixis in Brownie Lake is largely anthropogenic, whereas in Canyon Lake it is natural; (4) the shallow chemocline of Brownie Lake and high phosphorus reservoir make it an ideal analog to study anoxygenic photosynthesis, elemental ratios, and mineralogy; and (5) a deep penetrating suboxic zone in Canyon Lake may support future studies of suboxic microbial activity or mineral transformation.

Pigment carbon and nitrogen isotopic signatures in euxinic basins.

The carbon and nitrogen isotopic signatures of chloropigments and porphyrins from the sediments of redox-stratified lakes and marine basins reveal details of past biogeochemical nutrient cycling. Such interpretations are strengthened by modern calibration studies, and here, we report on the C and N isotopic composition of pigments and nutrients in the water column and surface sediment of redox-stratified Fayetteville Green Lake (FGL; New York). We also report δ13 C and δ15 N values for pyropheophytin a (Pphe a) and bacteriochlorophyll e (Bchl e) deposited in the Black Sea during its transition to a redox-stratified basin ca. 7.8 ka. We propose a model for evolving nutrient cycling in the Black Sea from 7.8 to 6.4 ka, informed by the new pigment data from FGL. The seasonal study of water column nutrients and pigments at FGL revealed population dynamics in surface and deep waters that were also captured in the sediments. Biomass was greatest near the chemocline, where cyanobacteria, purple sulfur bacteria (PSB), and green sulfur bacteria (GSB) had seasonally variable populations. Bulk organic matter in the surface sediment, however, was derived mainly from the oxygenated surface waters. Surface sediment pigment δ13 C and δ15 N values indicate intact chlorophyll a (Chl a) was derived from near the chemocline, but its degradation product pheophytin a (Phe a) was derived primarily from surface waters. Bacteriopheophytin a (Bphe a) and Bchl e in the sediments came from chemocline populations of PSB and GSB, respectively. The distinctive δ13 C and δ15 N values for Chl a, Phe a, and Bphe a in the surface sediment are inputs to an isotopic mixing model that shows their decomposition to a common porphyrin derivative can produce non-specific sedimentary isotope signatures. This model serves as a caveat for paleobiogeochemical interpretations in basins that had diverse populations near a shallow chemocline.

Marine redox evolution in the early Cambrian Yangtze shelf margin area: evidence from trace elements, nitrogen and sulphur isotopes

AbstractNitrogen is an essential element for biological activity, and nitrogen isotopic compositions of geological samples record information about both marine biological processes and environmental evolution. However, only a few studies of N isotopes in the early Cambrian have been published. In this study, we analysed nitrogen isotopic compositions, as well as trace elements and sulphur isotopic compositions of cherts, black shales, carbonaceous shales and argillaceous carbonates from the Daotuo drill core in Songtao County, NE Guizhou Province, China, to reconstruct the marine redox environment of both deep and surface seawater in the study area of the Yangtze shelf margin in the early Cambrian. The Mo–U covariation pattern of the studied samples indicates that the Yangtze shelf margin area was weakly restricted and connected to the open ocean through shallow water flows. Mo and U concentrations, δ15Nbulk and δ34Spy values of the studied samples from the Yangtze shelf margin area suggest ferruginous but not sulphidic seawater and low marine sulphate concentration (relatively deep chemocline) in the Cambrian Fortunian and early Stage 2; sulphidic conditions (shallow chemocline and anoxic photic zone) in the upper Cambrian Stage 2 and lower Stage 3; and the depression of sulphidic seawater in the middle and upper Cambrian Stage 3. Furthermore, the decreasing δ15N values indicate shrinking of the marine nitrate reservoir during the middle and upper Stage 3, which reflects a falling oxygenation level in this period. The environmental evolution was probably controlled by the changing biological activity through its feedback on the local marine environment.

Patterns of local and global redox variability during the Cenomanian–Turonian Boundary Event (Oceanic Anoxic Event 2) recorded in carbonates and shales from central Italy

AbstractCareful evaluation of the local geochemical conditions in past marine settings can provide a window to the average redox state of the global ocean during episodes of extensive organic carbon deposition. These comparisons aid in identifying the interplay between climate and biotic feedbacks contributing to and resulting from these events. Well‐documented examples are known from the Mesozoic Era, which is characterized by episodes of widespread organic carbon deposition known as Oceanic Anoxic Events. This organic carbon burial typically leads to coeval positive carbon‐isotope excursions. Geochemical data are presented here for several palaeoredox proxies (Cr/Ti, V, Mo, Zn, Mn, Fe speciation, I/Ca and sulphur isotopes) from a section exposed at Furlo in the Marche–Umbrian Apennines of Italy that spans the Cenomanian–Turonian boundary. Here, Oceanic Anoxic Event 2 is represented by a ca 1 m thick radiolarian‐rich millimetre‐laminated organic‐rich shale known locally as the Bonarelli Level. Iron speciation data for thin organic‐rich intervals observed below the Bonarelli Level imply a local redox shift going into the Oceanic Anoxic Event, with ferruginous conditions (i.e. anoxic with dissolved ferrous iron) transiently developed prior to the event and euxinia (i.e. anoxic and sulphidic bottom waters) throughout the event itself. Pre‐Oceanic Anoxic Event enrichments of elements sensitive to anoxic water columns were due to initial development of locally ferruginous bottom waters as a precursor to the event. However, the greater global expanse of dysoxic to euxinic conditions during the Oceanic Anoxic Event greatly reduced redox‐sensitive trace‐metal concentrations in seawater. Pyrite sulphur isotopes document a positive excursion during the Oceanic Anoxic Event. Carbonate I/Ca ratios were generally low, suggesting locally reduced bottom‐water oxygen conditions preceding the event and relatively increased oxygen concentrations post‐event. Combined, the Furlo geochemical data suggest a redox‐stratified water column with oxic surface waters and a shallow chemocline overlying locally ferruginous bottom waters preceding the event, globally widespread euxinic bottom waters during the Oceanic Anoxic Event, followed by chemocline shallowing but sustained local redox stratification following the event.

Trace and rare earth elemental geochemistry of carbonate succession in the Middle Gaoyuzhuang Formation, Pingquan Section: Implications for Early Mesoproterozoic ocean redox conditions

The concentrations of redox-sensitive trace elements, such as uranium (U), vanadium (V), molybdenum (Mo), cobalt (Co), chromium (Cr) and rare earth elements (REE+Y) were determined in a given carbonate succession in the Gaoyuzhuang Formation (~1.56 Ga), which spans depths from outer shelf to intertidal, to explore the Early Mesoproterozoic ocean redox conditions. The values of the Zr-normalized redox-sensitive trace element concentrations and some relevant ratios show obvious changes from bottom to top in the succession. Samples from the outer shelf setting (M1 interval) demonstrate significantly enhanced values in Zr-normalized redox-sensitive trace element concentrations and relevant ratios (the peaks of Mo/U, V/Cr and Ni/Co ratios larger than 8, 4.25, and 7, respectively). Authigenic framboidal pyrites were also found within oncolite-like carbonate concretions and surrounding host rocks in this interval. These all indicate a euxinic state in the outer shelf environment. Less enrichment of Zr-normalized redox-sensitive elemental abundances and a mild decrease in the values of geochemical ratios were present in the inner shelf environment (M2 interval) (the V/Cr and Ni/Co ratios fall into a range of 2.5-4.25 and 4-5, respectively), suggesting dysoxic conditions dominant in the inner shelf setting. Samples from the shallower subtidal and intertidal settings (M3 and M4 intervals) are mostly invariable with much lower values of Zr-normalized redox-sensitive elements and relevant ratios, with the V/Cr and Ni/Co ratios typically near or less than 2 and 5 respectively, indicative of oxic conditions in the high-energy subtidal/intertidal zones. A remarkable negative Ce anomaly exhibited in the shale-normalized REE+Y diagram in the M4 interval may provide evidence in support of the hypothesis. Taken together, our results suggest a relatively shallow chemocline in the Early Mesoproterozoic ocean: the transitions between euxinic, dysoxic and oxic may occur in quiet-water outer shelf and highenergy subtidal zone, respectively. The presence of euxinic ocean bottom waters is compatible with low concentrations of seawater sulfate and reduced levels of atmospheric oxygen during this period. The extreme environmental conditions induced by these anoxic oceans could have been responsible for the delayed oxygenation of the biosphere and hindered the evolution of multicellular life.

Compound-specific carbon isotope study on the hydrocarbon biomarkers in lacustrine source rocks from Songliao Basin

Stable carbon isotopic composition of organic matter (δ13Corg) and compound-specific δ13C values of biomarkers from 15 lacustrine source rocks were analyzed to identify the original paleoenvironment and source organisms. The δ13C values of hopanes (δ13Chop) ranged from −68.7‰ to −32‰ and exhibit strongly 13C-depleted values in the lower part of Member 1 of the Nenjiang Formation (K2n1, up to −68.7‰), suggesting an origin from predominantly methanotrophic bacteria. 13C-enriched δ13CGa values and significantly 13C-depleted δ13Chop in K2n1, which coincide with water stratification and an intermittent anoxic photic zone, represents a shallow chemocline. The presence of an intermittent anoxic photic zone, which means that the anoxia expanded into the euphotic zone, is beneficial for OM preservation and results in high values of TOC and HI in this section. However, the absence of gammacerane and 13C-enrichment of δ13Chop in Member 2 of Nenjiang Formation (K2n2) reflect a deeper chemocline, corresponding to relatively oxidizing conditions and low values of TOC and HI. Moreover, the negative correlation of TOC vs δ13Corg and HI vs δ13Corg reflects the control of OM formation by sedimentary environments rather than productivity in the water column. Thus, the depth of the chemocline not only controls the abundance of OM but also affects the development of the microbial community, such as chemoautotrophic bacteria in the deep chemocline and chemoautotrophic and methanotrophic bacteria in the shallow chemocline. Moreover, δ13CGa and δ13C values for 4-methyl steranes are related to water salinity, with a higher salinity accompanied by 13C-enrichment in gammacerane and 4-methyl steranes.

Organomineralization in Mesoproterozoic giant ooids

Ooids are common carbonate particles that are traditionally considered as abiogenically formed by physical and chemical processes in highly agitated environments. Recent studies point to the importance of microbial activities in ooid formation, but more case studies are required to confirm and clarify the roles of microbes and their organomineralization processes. Here we report an integrated petrographic, element geochemical, and isotopic study of Mesoproterozoic giant ooids from the Wumishan Formation (ca. 1.50–1.45Ga) of North China. The Wumishan giant ooids (2.0–14.4mm) are composed of small micritic nuclei and thick radial fibrous cortices. Abundant organic relics, including putative bacterial filaments and mucus-like extracellular polymeric substances (EPS), are present in ooid cortices. Organominerals (e.g., nanoparticles and polyhedrons) are concentrated and lined with the axes of radial fibers, suggesting in situ mineralization of bacterial filaments. The abundance of organic relics and fiber-aligned organominerals confirms the constructive roles of microbes in the formation of the Wumishan giant ooids. The preservation of bacterial filaments/filament bundles in their growth orientation requires fast mineralization in CaCO3-supersaturated environments, which may have been controlled by the shallow chemocline in redox-stratified Mesoproterozoic basins.

Heterogeneous redox conditions and a shallow chemocline in the Mesoproterozoic ocean: Evidence from carbon–sulfur–iron relationships

Oxygenation of Earth's oceans in the Proterozoic was a protracted process that began prior to the Great Oxidation Event (GOE) and culminated in deep ocean ventilation following Neoproterozoic glacial episodes, with both of these major thresholds accompanied by profound changes in the evolution of Earth's biosphere. Our understanding of the redox structure of Mesoproterozoic oceans, however, is considerably less certain. Limited proxy investigations of oceanic redox in the Mesoproterozoic have focused largely on early Mesoproterozoic shelf to basinal settings, with comparatively little attention paid to epeiric sea environments that dominate the late Mesoproterozoic sedimentary record. Here we report multi-proxy shale redox data from epicratonic and pericratonic environments of the 1.1Ga Atar and El Mreiti Groups, Taoudeni Basin, Mauritania. These strata were deposited across the West African craton during global sea level highstand, and provide insight into the redox structure of Mesoproterozoic epeiric seas. Iron speciation, pyrite sulfur isotope, and trace metal concentration data suggest a shallow chemocline and highly heterogeneous redox conditions, with fundamental heterogeneities in sulfate concentration and the extent and persistence of euxinia between onshore and offshore environments. We suggest that a protracted increase in biospheric oxygenation in the late Mesoproterozoic was accompanied by unstable and heterogeneous redox conditions in shallow, nearshore areas, contributing to the fragmentary pattern of early eukaryotic evolution and diversification.

Shallow stratification prevailed for ∼1700 to ∼1300 Ma ocean: Evidence from organic carbon isotopes in the North China Craton

The Late Paleoproterozoic to Early Mesoproterozoic (from ∼1700 Ma to ∼1300 Ma) was highlighted by the assembly of the Nuna supercontinent, expansion of euxinic marine environments and apparent stasis in the diversity of eukaryotes. The isotopic composition of carbonate carbon (δ13Ccarb) was surprisingly constant during this interval, but little is known about the secular variation in the organic carbon isotopic composition (δ13Corg). Here we report δ13Corg data from the latest Paleoproterozoic (>1650 Ma) to Early Mesoproterozoic (∼1300 Ma) succession in North China. The δ13Corg values range from −25‰ to −34‰, and are dependent on sedimentary facies. In subtidal and deeper environments δ13Corg values are low and constant, ca. −32‰, but relatively enriched and more variable in shallower intertidal and supratidal environments. We attribute the facies-dependent variation in δ13Corg to the presence of a shallow chemocline. A probable result of a shallow chemocline is that it supported significant contributions of organic matter produced by chemoautotrophic and/or anaerobic photoautotrophic microbes in relatively deep environments from the latest Paleoproterozoic to Early Mesoproterozoic continental shelf of North China.

Oceanic molybdenum drawdown by epeiric sea expansion in the Mesoproterozoic

Molybdenum is a bioessential micronutrient whose abundance in the global oceans may have played a primary role in evolution of the Earth's nitrogen cycle and, ultimately, in the timing of the ecologic expansion of early eukaryotes. Because molybdenum (Mo) is delivered to the ocean under conditions of oxic weathering and is removed in suboxic and euxinic environments, the concentration of Mo in the oceans reflects a complex function of global redox and the hydrologic conditions that influence the areal extent of euxinic sedimentation. Recent compilations of Mo within euxinic shales (Scott et al., 2008; Och and Shields-Zhou, 2012; Sahoo et al., 2012) indicate that the oceanic reservoir of Mo did not rise substantially above crustal values until the Great Oxidation Event (~2.3Ga), and a modern Mo cycle did not develop until the contraction of ocean euxinia in the latest Proterozoic.At present, a paucity of data from euxinic shales of the late Mesoproterozoic (1.3 to 1.0Ga) limits our ability to relate marine redox evolution to biological innovation during a critical interval of eukaryotic development. Here we present data from marine shales of the 1.1Ga Atar and El Mreiti groups, Mauritania, which were deposited during sea level highstand when shallow, epeiric seas covered much of the West African craton. Epicratonic strata of the El Mreiti Group were deposited under fluctuating redox conditions near a shallow chemocline (as evidenced by iron speciation), and record generally low Mo concentrations (<15ppm) and Mo/TOC ratios (<2ppm/wt.%), along with a weak covariance between Mo and TOC. By contrast, craton margin strata of the coeval Atar Group were deposited under relatively persistent euxinic conditions, yet record Mo concentrations largely <1ppm and show no covariance between Mo and TOC. Combined, data suggest that Mo sourced from terrestrial weathering was preferentially sequestered in proximal regions of the epeiric sea, and that onshore sequestration led directly to critically low Mo concentrations in offshore waters. We suggest that a Mesoproterozoic expansion of nearshore euxinia (at least in pore waters) within epeiric seas led directly to a critical depletion of the global oceanic Mo reservoir. This hypothesis is supported by a series of first-order sensitivity tests that estimate the extent to which expansion of epeiric seas would have drawn down oceanic Mo concentrations. Ultimately, this study suggests that substantial lateral redox heterogeneity may have limited the availability of bioessential trace metals in the Mesoproterozoic oceans, despite evidence for increased biospheric oxygenation. Extreme Mo limitation in open oceans environments would have had profound effects on the global nitrogen cycle and may help explain observed onshore–offshore patterns in early eukaryotes.

The role of surface water and mine groundwater in the chemical stratification of an acidic pit lake (Iberian Pyrite Belt, Spain)

• The lake is made up by mine groundwater and surface water and is in hydraulic balance. • The different sources of recharge at lake cause the meromixis in spite of little depth. • In winter the runoff inflow thickens mixolimnion and the system losses groundwater. • In summer the evaporation slims mixolimnion and the lake gains groundwater. • A conceptual model explaining its seasonal limnological evolution is advanced. The hydraulic system of the Concepción mine is made up of an open pit and an underground mine, which are currently flooded and hydraulically connected. The Concepción pit lake has shown permanent chemical stratification (meromictic lake), where two layers with different density and chemical composition can be differentiated: (i) a thick superficial layer of 11 ± 2 m deep, with a low concentration of dissolved solids (mixolimnion) and (ii) a thin bottom layer from 11 ± 2 m to 16 m deep (monimolimnion), exhibiting vertical changes in its physico-chemical parameters, with decreasing redox potential and increasing T, pH and dissolved solids content with depth. The distribution of the Concepción pit lake layers depends on recharge processes and the loss of water from the system. In winter, rainfall and runoff result in a rapid increase of lake levels. The lake regains its initial level whenever water is lost through an old mine adit, since galleries and shafts act as preferential pathways for inflowing and outflowing water. This network is connected to the bottom of the lake, resulting in the progressive downward movement of the chemocline. Furthermore, runoff generates a less dense superficial layer, which triggers the development of an ephemeral chemocline in the mixolimnion. In summer, the mixolimnion loses water by evaporation which is partially compensated by groundwater inflowing from the lake bottom, resulting in the upward movement of the permanent chemocline. During this period the water level in the system is below the outlet level, which therefore renders the outflow of water inactive. During this stage, the mixolimnion remains homogeneous and the shallow chemocline disappears. Taking into consideration the hydrochemical characteristics of this pit lake and the spatial distribution of the layers identified, a model that explains its seasonal limnological evolution is presented.

Origins of enigmatic C-3 methyl and C-3 H porphyrins in ancient sediments revealed from formation of pyrophaeophorbide d in simulation experiments

The reaction of methyl pyrophaeophorbide a with hydrogen sulfide and oxygen under mild conditions (low temperature, moderate pH), which resemble those in certain natural environments, leads to its near quantitative conversion into methyl pyrophaeophorbide d (82–89%). The transformation, via oxidative cleavage of the C-3 vinyl substituent of pyrophaeophorbide a to afford an aldehyde at C-3, results from co-oxidation of the vinyl group and hydrogen sulfide by molecular oxygen. The co-oxidation transformation pathway operating on vinyl substituted chlorophyll derivatives can explain the origins of C-3 methyl and C-3 H porphyrins in ancient sediments and oils, structures for which the origins were previously unresolved. Evaluation of previous reports of C-3 methyl and C-3 H porphyrins in ancient sediments and oils reveals that their distributions are consistent with insights provided from analysis of the reaction mechanisms revealed by the laboratory studies. Thus, the sedimentary distributions reveal key features of the depositional settings, in particular the presence of a deep or a shallow chemocline. The oxidative cleavage of the C-3 vinyl group also provides insight into the biosynthesis of chlorophyll d by the cyanobacterium Acaryochloris marina, and offers a mild alternative to classical methods for the synthetic manipulation of the vinyl substituents of tetrapyrroles.

Lacustrine source rock deposition in response to co-evolution of environments and organisms controlled by tectonic subsidence and climate, Bohai Bay Basin, China

Three Paleogene syn-rift intervals from the Bohai Bay Basin, the most petroliferous basin in China, were analyzed with sedimentological and geochemical techniques to characterize the lateral source rock heterogeneities, to reveal the environmental and ecological changes through geologic time and to construct depositional models for lacustrine source rocks under different tectonic and climatic conditions. The third (Es 3) and first (Es 1) members of the Eocene Shahejie Formation and the Oligocene Dongying Formation (Ed) display widely variable total organic carbon contents, hydrogen indices and visual kerogen compositions, suggesting changes in organic facies from deep to marginal sediments. Carefully selected deep-lake facies samples from any interval, however, display fairly uniform biomarker composition. These three intervals have distinctly different biomarker assemblages, which indicate weakly alkaline, freshwater lakes with a moderately deep thermocline during Es 3 deposition, alkaline-saline lakes with shallow chemocline during Es 1 deposition and acidic, freshwater lakes with deep, unstable thermocline during the deposition of the Dongying Formation. Such environmental changes corresponded to changes in subsidence rate and paleoclimate, from rapid subsidence and wet climate during Es 3 deposition, through slow subsidence and arid climate during Es 1 deposition to rapid subsidence and wet climate during Ed deposition and resulted in synchronous changes in terrigenous organic matter input, phytoplankton community and primary productivity. The co-evolution of environments and organisms controlled by tectonic subsidence and climate accounted for the deposition and distribution of high quality lacustrine source rocks with distinctly different geochemical characteristics. Most rift basins experienced changes in subsidence rates and possibly changes in climates during their syn-rift evolutions. The models constructed in this paper may have important implications for source rock prediction in other lacustrine rift basins.

Evolution of the oceanic sulfur cycle at the end of the Paleoproterozoic

Here, we present new measurements of 32S, 33S, 34S, and 36S in sedimentary sulfides and couple these measurements with modeling treatments to study the sulfur cycle of a late Paleoproterozoic marine basin. We target the transition in ocean chemistry from the deposition of Paleoproterozoic iron formations (Gunflint Formation, Biwabik Formation, Trommald Formation, and Mahnomen iron formations) to the inferred sulfidic ocean conditions recorded by overlying shale (Rove Formation). The data suggest that certain features of the global sulfur cycle, such as a control by sulfate reducing prokaryotes, and low (mM) concentrations of oceanic sulfate, were maintained across this transition. This suggests that the transition was associated with changes in the structure of the basin-scale sulfur cycle during deposition of these sediments. Sulfide data from the iron formations are interpreted to reflect sedimentary sulfides formed from microbial reduction of pore-water sulfate that was supplied through steady-state exchange with an overlying oceanic sulfate reservoir. The sulfide data for the euxinic Rove Formation shales reflect the operation of a sulfur cycle that included the loss of sulfide by a Rayleigh-like process. We suggest that the prevalence of large and variable heavy isotope enrichments observed in Rove Formation sulfide minerals reflect a sustained and significant net loss of sulfide from the euxinic water column, either as a result of a shallow chemocline and degassing to the atmosphere or as a result of a water column pyrite sink. The inclusion of 36S measurements (in addition to 32S, 33S, and 34S) illustrates the mass-dependent character of these sedimentary environments, ruling out contributions from the weathering of Archean sulfides and pointing to at least modest levels of sustained atmospheric oxygen (>10 −5 present atmospheric levels of O 2).