Water Column Redox Conditions Research Articles

Re‐Evaluating Water Column Reoxygenation During the End Permian Mass Extinction

AbstractOcean anoxia is considered a key driver of the end‐Permian mass extinction (EPME). However, it is much debated whether there was an ocean reoxygenation phase during, and in the aftermath, of the EPME. Evidence for ocean reoxygenation is often inferred from the absence of framboidal pyrite in some boundary marine sediments (termed the “framboid gap”). To reconstruct ocean redox evolution across the EPME, we investigated the carbon isotopic, sedimentological, and redox records of the Ruichang and Ehtan sections in South China. These documents two negative δ13Ccarb excursions and the development of anoxia associated with deepening leading up to the Permian‐Triassic boundary. Above the level at which most siliceous organisms became extinct, pyrite framboid and iron proxies indicate that water column redox conditions were predominantly oxygenated but sporadically anoxic/ferruginous [non‐sulfidic, free Fe(II) in the water] at Ruichang, while ferruginous conditions were more widely developed at Ehtan. These contrasting redox states are characteristic of a dynamic ocean redox landscape in the extinction interval. The “framboid gap” is seen in strata deposited under both oxic and ferruginous conditions, suggesting that the availability of decomposable organic matter for sulfate reduction additionally controlled framboid genesis. Our data confirm that oxygenated conditions were developed in some deep water basins during the EPME.

Eutrophication and Deoxygenation Drive High Methane Emissions from a Brackish Coastal System.

Coastal environments are a major source of marine methane in the atmosphere. Eutrophication and deoxygenation have the potential to amplify the coastal methane emissions. Here, we investigate methane dynamics in the eutrophic Stockholm Archipelago. We cover a range of sites with contrasting water column redox conditions and rates of organic matter degradation, with the latter reflected by the depth of the sulfate-methane transition zone (SMTZ) in the sediment. We find the highest benthic release of methane (2.2-8.6 mmol m-2 d-1) at sites where the SMTZ is located close to the sediment-water interface (2-10 cm). A large proportion of methane is removed in the water column via aerobic or anaerobic microbial pathways. At many locations, water column methane is highly depleted in 13C, pointing toward substantial bubble dissolution. Calculated and measured rates of methane release to the atmosphere range from 0.03 to 0.4 mmol m-2 d-1 and from 0.1 to 1.7 mmol m-2 d-1, respectively, with the highest fluxes at locations with a shallow SMTZ and anoxic and sulfidic bottom waters. Taken together, our results show that sites suffering most from both eutrophication and deoxygenation are hotspots of coastal marine methane emissions.

Reduction in Marine Primary Productivity in the Early Cambrian Nanhua Basin, South China.

The Cambrian explosion is represented by a rapid diversification of early animals in which the role of marine primary productivity remains obscure. In this study, we analyzed multiple geochemical data, including TOC, major, and trace elements, in the basinal Yuanjia section, South China. Covariations among TOC, P/Al, CuEF, and NiEF suggest that they could be taken as effective marine productivity proxies in the early Cambrian Nanhua Basin. The similarities of CdEF and Cd/Mo in the Nanhua Basin and modern upwelling settings suggest that they might be effective to track upwelling, where Cd and Mo were mainly controlled by plankton biomass and redox conditions, respectively. Our results indicate that CoEF and Co × Mn were invalid in evaluating upwelling because of the significant effects of water-column redox conditions on Co enrichments in the Nanhua Basin. The decreased TOC, P/Al, CuEF, and NiEF reflect a long-term decline in marine productivity from late age 2 to age 3. In comparison with the published results in the outer shelf (Jinsha, TZS drill core, YJK drill core, and GDM-1 well) and slope areas (TX-1 well), the fall in marine productivity might be common in the early Cambrian Nanhua Basin. Our results exhibit that the reduced marine productivity was accompanied by weakened upwelling, quiet hydrothermal activities, and enhanced local terrestrial fluxes, indicating that variations in marine productivity might be mainly driven by the development of upwelling in the early Cambrian Nanhua Basin. Comparison of marine productivity with fossil records suggests that food availability was sufficient to sustain the Cambrian explosion in the Nanhua Basin. We infer that marine productivity might indirectly stimulate early animal evolution through its significant impact on water-column oxygen levels in the early Cambrian Nanhua Basin.

Climate variability during the late Ediacaran: Insights from episodic deposition of black shale-hosted Mn‑carbonates in South China

The Ediacaran period witnessed events that were of significance to the evolution of Earth's environment and early life, especially the Neoproterozoic Oxygenation Event during the Shuram Event (ca. 570–562 Ma) that was followed by the rise of animal life. However, the nature of the climate change that followed the Shuram Event in South China remains unclear. Black shale-hosted Mn‑carbonate deposits have the potential to reveal valuable information about paleo-seawater conditions and paleoclimate. This paper presents results of an investigation of the unique Ediacaran mudstone succession of South China, especially black shale-hosted Mn‑carbonate deposits, and offers a new perspective of the interconnected nature of paleoclimate and Ediacaran deposits. Relying on detailed petrological, sedimentological, and geochemical data, we posit that Ediacaran Mn‑carbonates accumulated in a semi-enclosed basin that experienced oscillating water column redox conditions and enhanced primary productivity. Chemical index of alteration (CIA) values, Rb/Sr ratios, and δ13C − δ15N stratigraphy of the analyzed deposits provide evidence of episodic warming during an otherwise protracted cooling trend following the Shuram Event (ca. 562–551 Ma). This study highlights the significant utility of black shale-hosted Mn‑carbonate strata in reconstructing Earth's paleoclimate during transitions.

Environmental controls on the distribution of GDGT molecules in Lake Höglwörth, Southern Germany

Tetraether lipids, such as glycerol dialkyl glycerol tetraethers (GDGTs), are an increasingly used proxy for reconstructing paleoclimatic and paleoenvironmental dynamics. On a global scale, environmental drivers controlling the distribution of GDGTs in lake systems have been described extensively. However, the drivers that control down-core sedimentary GDGT composition within single lake systems are still poorly constrained. Here, we analysed GDGTs in a sediment core collected from Lake Höglwörth (Bavaria, Germany) covering the last ∼1100 years. The increase in ratio ΣIIIa/ΣIIa values (a ratio which captures the variation of 3 structural isomers of penta- and hexamethylated brGDGTs respectively) reflects a higher contribution of branched (br) GDGTs from aquatic sources after 1800 CE. This is synchronous with a high nutrient input as a result of increased local anthropogenic activities. The climate proxy methylation of branched tetraethers (MBT'5ME) reveals a pattern that deviates from the anticipated temperature changes during the last millennium. Instead, high MBT'5ME values from ∼880 to 1120 CE coincide with a period of increased soil input, resulting from lake damming and/or construction of the Höglwörth monastery. Decreased values after 1800 CE until present date correspond to a higher contribution of aquatic brGDGTs, with changes in the dependency between Ia and IIa suggesting a direct influence of bacterial community changes on the MBT'5ME. The proxy cyclisation of branched tetraethers (CBT') shows a linear increase with time, and a stepwise increase at 1700 CE, when a creek stream inflow channel was rerouted. Over time, MBT’5ME decreases gradually, while CBT’ and ΣIIIa/ΣIIa increase. This is hypothesized to be potentially caused by decreasing water depth over time and/or post- or syn-sedimentary production of GDGTs. The degree of cyclization (DC') shows variations on shorter timescales, possibly driven by the lake mixing regime and water column redox conditions. Our results indicate that caution must be taken when interpreting GDGTs for paleoclimate and paleoenvironmental reconstruction considering the possible influence of shifts in the provenance of brGDGTs. Further studies focusing on both sedimentary and intact polar lipids are highly recommended to constrain the source (water column, or sedimentary production) of GDGTs in lake sediments.

Spatiotemporal Evolution and Genesis of the Late Ordovician—Early Silurian Marine Euxinia in Northeastern Upper Yangtze Basin, South China

Marine redox conditions and their dynamic changes were a major factor that controlled the formation of black shale and caused the late Ordovician marine extinction in the Upper Yangtze Basin (South China). However, the spatiotemporal variation and potential controlling factors of marine redox conditions in this area remain unclear. We analyzed whole-rock geochemistry and pyrite sulfur isotopes (δ34Spy) of 47 shale samples from the Late Katian to Rhuddanian in a shelf-to-slope (Qianjiang Shaba section and Wc-1 well) region of northeastern Upper Yangtze Basin, and reconstructed water column redox conditions during the Late Ordovician–Early Silurian Transition. The geochemical characteristics of shale, including the ratio of elements, discriminant function and ternary diagram location in the study area suggest a passive continental margin sedimentary environment, wherein the terrigenous detritus is mainly derived from felsic igneous rocks in the upper crust, showing characteristics of near-source deposition. The redox indices (Fe speciation, Corg/P, UEF, and MoEF) showed that the development of anoxic water, especially euxinia, has obvious spatiotemporal heterogeneity. Under conditions of high availability of active organic carbon and limited sulfate supply, high active Fe input and strong biological irrigation in the shallow water area may effectively remove H2S produced by microbial sulfate reduction, conducive to the prevalence of ferruginous water columns. However, for this deep water area, the rapid accumulation rate of organic matter, decrease in dissolved Fe (caused by upwelling in the open sea), and seawater stratification (caused by the rising of sea level) promoted the development of a euxinic water column. This inference is supported by the covariant relationship between organic carbon accumulation rate, chemical index of alteration, Co × Mn, and δ34Spy. Our study highlights the potential control effects of sea level change, continental weathering and upwelling on the development of euxinic water columns.

The Ediacaran ‘Miaohe Member’ of South China: new insights from palaeoredox proxies and stable isotope data

AbstractThroughout the Ediacaran Period, variable water-column redox conditions persisted along productive ocean margins due to a complex interplay between nutrient supply and oceanographic restriction. These changing conditions are considered to have influenced early faunal evolution, with marine anoxia potentially inhibiting the development of the ecological niches necessary for aerobic life forms. To understand this link between oxygenation and evolution, the combined geochemical and palaeontological study of marine sediments is preferable. Located in the Yangtze Gorges region of southern China, lagoonal black shales at Miaohe preserve alga and putative metazoans, including Eoandromeda, a candidate total-group ctenophore, thereby providing one example of where integrated study is possible. We present a multi-proxy investigation into water-column redox variability during deposition of these shales (c. 560–551 Ma). For this interval, reactive iron partitioning indicates persistent water-column anoxia, while trace metal enrichments and other geochemical data suggest temporal fluctuations between ferruginous, euxinic and rare suboxic conditions. Although trace metal and total organic carbon values imply extensive basin restriction, sustained trace metal enrichment and δ15Nsed data indicate periodic access to open-ocean inventories across a shallow-marine sill. Lastly, δ13Corg values of between −35‰ and −40‰ allow at least partial correlation of the shales at Miaohe with Member IV of the Doushantuo Formation. This study provides evidence for fluctuating redox conditions in the lagoonal area of the Yangtze platform during late Ediacaran time. If these low-oxygen environments were regionally characteristic, then the restriction of aerobic fauna to isolated environments can be inferred.

Chromium isotope heterogeneity on a modern carbonate platform

Chromium isotope (δ53Cr) values of marine sedimentary rocks are increasingly utilised for monitoring changes in redox conditions in the Earth's ancient oceans and atmosphere. Carbonate rocks are of particular interest as they are relatively common in the sedimentary record and have been shown under laboratory conditions to be capable of recording the Cr isotope composition of precipitating fluids. However, little data from appropriate modern analogues is currently available to constrain the variability in δ53Cr values within a carbonate platform and slope system and assess the preservation potential of marine δ53Cr values during burial, lithification and diagenesis. In this paper we investigate the heterogeneity of δ53Cr values on a modern marine carbonate platform in the context of carbonate sediment deposition, mineralogy, and the influence of burial and early lithification. We present new δ53Cr values from carbonate sediments in the upper 200 m of ODP Leg 166 Site 1003 taken from the western margin of the Great Bahama Bank (GBB) and compare these data to modern carbonate sediments accumulating on the GBB platform-top. Shallow-water surface sediments record a range of heavy δ53Cr values from +0.77 to +1.07‰ while drill core samples record a larger range of δ53Cr values from +0.51 to +0.97‰. Down-core variability in δ53Cr values occurs systematically with changes in sediment composition and mineralogy, where more positive δ53Cr values occur in drill core samples that preserve proportionally more banktop-derived carbonate and less well developed diagenetic textures. These values decrease down-core where proportionally more pelagic carbonate exists, and with increasing neomorphism of primary aragonite to low-Mg calcite. The mineralogical dependence of δ53Cr values at Site 1003 appears to be related to variations in relative sea-level across the platform and the degree of lithification and diagenetic recrystallization with depth, rather than in response to changes in the δ53Cr composition of the overlying water column. As the GBB represents a reasonable modern analogue for many Phanerozoic and Precambrian carbonate successions, the preliminary framework presented here may have significant implications for the interpretation of vertical profiles of δ53Cr values in paleo-redox studies. In particular, smaller scale variability in ancient carbonate sections can be more simply explained by local variations in depositional environment and diagenetic regime rather than fluctuations in water column redox conditions.

Reconstructing oxygen deficiency in the glacial Gulf of Alaska: Combining biomarkers and trace metals as paleo-redox proxies

Marine anaerobic oxidation of ammonium (anammox) plays a central role in the nitrogen cycle of modern Oxygen Deficient Zones (ODZs). The newly developed bacteriohopanetetrol stereoisomer (BHT-x) biomarker for anammox, which is largely unaffected by early diagenesis, allows for the reconstruction of the presence and dynamics of past ODZs from the sedimentary record of continental margins. In this study, we investigate the development and dynamics of the ODZ in the Gulf of Alaska (GOA) between 60 and 15 cal ka BP using records of redox sensitive trace metals (TM) and the BHT-x anammox biomarker from IODP Site U1419 (~700 m water depth). The biomarker record indicates that the ODZ in the GOA was in concert with global climate fluctuations in the late Pleistocene. Anammox was more pronounced during warmer periods and diminished during cooler periods, as indicated by correlation with the δ18O signal obtained by the North Greenland Ice core Project (NGRIP). Trace metal enrichments, however, do not match the trend in BHT-x. Systematic metal enrichments in intervals where biomarkers point to more intense water column deoxygenation are not observed. We suggest that this proxy discrepancy was caused by environmental factors, other than water column redox conditions, with opposing effects on the TM and biomarker records. Two of the most widely used redox indicators, Mo and U, are not significantly enriched throughout the sediment record at Site U1419. Site U1419 experienced some of the highest sedimentation rates (100–1000 cm ka−1) ever reported for late Pleistocene continental margin sediments, leading to a continuous and rapid upward migration of the sediment-water interface. We suggest that despite water column and seafloor oxygen depletion, significant sedimentary enrichments of these redox sensitive trace metals were prevented by a limited time for their diffusion across the sediment-water interface and subsequent enrichment as authigenic phases. Thus, depositional conditions were ideal for biomarker preservation but prevented significant authigenic trace metal accumulations. Similar discrepancies between organic and inorganic redox proxies could exist in other high sedimentation rate environments, potentially putting constraints on paleo-redox interpretations in such settings if they are based on trace metal enrichments alone.

Geochemical characteristics and organic matter enrichment mechanism of black shale in the Upper Triassic Xujiahe Formation in the Sichuan basin: Implications for paleoweathering, provenance and tectonic setting

Abstract The first, third and fifth members (henceforth referred to as T 3 x 1 , T 3 x 3 and T 3 x 5 , respectively) of the Upper Triassic coal-bearing Xujiahe Formation black shale are among the most significant hydrocarbon source rocks in the Sichuan basin. Here, we present geochemical data for the Upper Triassic black shales from core from Well LD-1 to determine their paleoenvironmental conditions, paleoweathering, provenance transitions and tectonic setting. The V/(V + Ni) vs. U/Th, V/Cr vs. U/Th and Ni/Co vs. U/Th bivariate plots and the TFe-TOC-TS (total Fe-total organic carbon-total Sulphur) ternary diagram indicate that the synsedimentary redox regime of almost all the shale samples was oxidizing. Ba/Al, Sr/Al and P/Ti data combined with quantitative biogenic Ba data indicate that moderate-high primary paleoproductivity levels prevailed during deposition. The Sr/Cu ratio and C-value combined with the sedimentary features are indicative of warm-humid climate conditions. The Ti/Al deposition rate proxy and decompacted sedimentation rate are positively correlated with the total organic carbon (TOC) content. According to our multiproxy approach, black shale development in the Xujiahe Formation was mainly controlled by the primary productivity level, foreland basin setting, high tectonic subsidence and sedimentation rate and exhibited a limited correlation with water column redox conditions. Through the compilation and calculation of various weathering indices for the Xujiahe black shale, we suggest that caution must be taken when inferring paleoclimate characteristics based on the chemical index of alteration (CIA) because of the influence of multiple nonweathering factors. Provenance-sensitive elemental ratios (Th/Sc vs. Zr/Sc and Co/Th vs. La/Sc) indicate that the clastic contribution to Xujiahe black shales was of a predominantly felsic character. The black shales exhibit a transition from T 3 x 1 to T 3 x 3 to T 3 x 5 , whereby T 3 x 1 was primarily sourced from the Proterozoic to early Paleozoic strata of the Qinling orogeny, T 3 x 3 was primarily sourced from the Neoproterozoic complex in the Longmen Shan, and T 3 x 5 was primarily sourced from the Songpan-Ganzi flysch strata, which contributed recycled material because of folding and strong southeastward thrusting.

Nitrogen isotope compositions of the Upper Triassic Chang 7 Shale, Ordos Basin, North China: Implications for depositional redox conditions

Nitrogen isotope (δ 15 N) analysis has been used to evaluate depositional redox conditions in well-preserved sedimentary systems; however, fewer N-isotope studies have been performed to reconstruct the redox conditions in lacustrine shales. In this paper, we report the δ 15 N data from the Upper Triassic Chang 7 Shale of the Ordos Basin, North China. Sedimentary δ 15 N values are significantly higher in the Chang 7 3 and the lower part of the Chang 7 2 submembers (Zone A; average = 9.4 ± 1.3‰) than in the upper part of the Chang 7 2 and the Chang 7 1 submembers (Zone B; average = 5.4 ± 1.5‰). Previous geochemical measurements (i.e., U and TOC/P) of both zones show wide redox variation, however, the average values of these redox proxies are relatively higher in Zone A than those of Zone B. Combined with lithological aspects of the Chang 7 Shale, our study suggest that Zone A was mainly deposited under suboxic bottom water conditions, whereas Zone B deposits accumulated within an oxygenated water column. Stable organic carbon isotopes (δ 13 C org ) and total nitrogen (TN) values of the two zones display little variation that could be attributed to changing organic matter sources and/or post-depositional alteration of δ 15 N. Thus, we suggest that variations in δ 15 N throughout the Chang 7 Shale primarily reflect differences in depositional redox conditions and δ 15 N values of the shale that can provide important details regarding the depositional history of unconventional resource plays. • Provide the first δ 15 N records of the Chang 7 Shale, Ordos Basin. • Differences in δ 15 N are primarily influenced by water column redox conditions. • Organic-rich intervals accumulated under suboxic conditions. • Tectonic events drove redox changes during deposition.

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.

Astronomically Driven Variations in Depositional Environments in the South Atlantic During the Early Cretaceous

AbstractThe extent and persistence of anoxia in the South Atlantic Ocean during its early opening phase in the Early Cretaceous is not well constrained, hindering a holistic understanding of the processes and mechanisms that drive past changes in water column redox conditions, as well as the impacts of such changes on marine ecosystems. Here we provide high‐resolution geochemical records from Deep Sea Drilling Project Site 364 that document variations in redox conditions, chemocline depth, marine productivity, and marine ecosystem dynamics in the northern South Atlantic during the Aptian. We show that many of these parameters varied across discrete sedimentary cycles expressed in the Deep Sea Drilling Project 364 succession. Our data indicate that during the initial stages of basin development, anoxic and euxinic conditions were prevalent and occasionally extended into the upper water column. However, strong cyclicity in sedimentological and geochemical parameters imply that the anoxia/euxinia was not a persistent state. We argue that the water column redox conditions during the Aptian were driven by changes in the hydrological cycle, induced by variations in astronomical forcing. We suggest that the episodically amplified hydrological cycle not only enhanced nutrient availability and marine productivity, but might also have caused density‐driven upper ocean stratification. The presence of black shales of similar age in other ocean basins suggests that this mechanism is broadly important for the formation of Early Cretaceous organic‐rich successions.

Controls on the evolution of Ediacaran metazoan ecosystems: A redox perspective

A growing number of detailed geochemical studies of Ediacaran (635–541 Ma) marine successions have provided snapshots into the redox environments that played host to the earliest known metazoans. Whilst previous compilations have focused on the global evolution of Ediacaran water column redox chemistry, the inherent heterogeneity evident in palaeogeographically distinct environments demands a more dissected approach to better understand the nature, interactions and evolution of extrinsic controls on the development of early macrobenthic ecosystems. Here, we review available data of local‐scale redox conditions within a palaeogeographic and sequence stratigraphic framework, to explore the mechanisms controlling water column redox conditions and their potential impact on the record of metazoans. The openly connected Laurentian margin, North America (632–540 Ma) and Nama basin, Namibia (550–538 Ma), and the variably restricted Yangtze Block, South China (635–520 Ma), show continued redox instability after the first fossil evidence for metazoans. This may support opportunistic benthic colonisation during periods of transient oxygenation amidst episodic upwelling of anoxic waters beneath a very shallow, fluctuating chemocline. The first skeletal metazoans appeared under conditions of continued redox stratification, such as those which characterise the Dengying Formation of the Yangtze Block and the Kuibis Subgroup of the Nama basin. Current data, however, suggests that successful metazoan reef‐building demanded more persistent oxia. We propose that cratonic positioning and migration throughout the Ediacaran Period, in combination with gradually increasing dissolved oxygen loading, may have provided a first‐order control on redox evolution through regulating circulation mechanisms in the Mirovian Ocean. Some unrestricted lower slope environments from mid‐high latitudes benefited from sustained oxygenation via downwelling, whilst transit of isolated cratons towards more equatorial positions stifled pervasive ventilation either through ineffective surface ocean mixing, Ekman‐induced upwelling, elevated surface ocean productivity or a combination of these processes.

Disentangling the record of diagenesis, local redox conditions, and global seawater chemistry during the latest Ordovician glaciation

The Late Ordovician stratigraphic record integrates glacio-eustatic processes, water-column redox conditions and carbon cycle dynamics. This complex stratigraphic record, however, is dominated by deposits from epeiric seas that are susceptible to local physical and chemical processes decoupled from the open ocean. This study contributes a unique deep water basinal perspective to the Late Ordovician (Hirnantian) glacial record and the perturbations in seawater chemistry that may have contributed to the Hirnantian mass extinction event. We analyze recently drilled cores and outcrop samples from the upper Vinini Formation in central Nevada and report combined trace- and major element geochemistry, Fe speciation (FePy/FeHR and FeHR/FeT), and stable isotope chemostratigraphy (δ13COrg and δ34SPy). Measurements of paired samples from outcrop and core reveal that reactive Fe is preserved mainly as pyrite in core samples, while outcrop samples have been significantly altered as pyrite has been oxidized and remobilized by modern weathering processes. Fe speciation in the more pristine core samples indicates persistent deep water anoxia, at least locally through the Late Ordovician, in contrast to the prevailing interpretation of increased Hirnantian water column oxygenation in shallower environments. Deep water redox conditions were likely decoupled from shallower environments by a basinal shift in organic matter export driven by decreasing rates of organic matter degradation and decreasing shelf areas. The variable magnitude in the record of the Hirnantian carbon isotope excursion may be explained by this increased storage of isotopically light carbon in the deep ocean which, in combination with increased glacio-eustatic restriction, would strengthen lateral- and vertical gradients in seawater chemistry. We adopt multivariate statistical methods to deconstruct the spatial and temporal re-organization of seawater chemistry during the Hirnantian glaciation and attempt to isolate the latent magnitude and global perturbation in the carbon cycle. We speculate, using a two component mixing model and residual estimates from principal component analysis, that the secular open ocean Hirnantian C isotope excursion possibly amounts to only ∼ +1.5‰. Such an increase could be mechanistically driven by the combination of sea-level fall, persistent deep water anoxia, and cooler glacial temperatures that increased the organic carbon burial efficiency in the deeper basins.

A Holocene history of dynamic water column redox conditions in the Landsort Deep, Baltic Sea

The modern Baltic Sea is the world9s largest anthropogenically forced anoxic basin. Using integrated geochemical records collected during Integrated Ocean Drilling Program (IODP) Expedition 347 from the deepest and one of the most reducing sub-basins in the Baltic Sea, Landsort Deep, we explore the degree and frequency of natural anoxia through the Baltic Holocene. A marked decrease in carbon-to-sulfur ratios (C/S) from the cores indicate the transition from the Baltic Ice Lake to the current brackish sea, which occurred about 8.5 kyrs B.P. Following this, laminations throughout sediments recording brackish deposition suggest sustained anoxia or extreme low oxygen, while high molybdenum (Mo) concentrations of >100 ppm and iron (Fe) geochemistry suggest water column sulfide accumulation, or euxinia, that persisted beyond seasonal timescales during deposition of two distinct sapropel units. Sedimentary Mo isotope values range from +1.11 to −0.50 permil, which are distinctly fractionated from modern Baltic seawater (+2.26 to +2.67‰) and thus indicate that each of the sapropels experienced only weak and/or oscillatory euxinia—in contrast to the more stable euxinic conditions of more restricted basins. A shift in δ98Mo starting above the lower sapropel to a distinctly more negative range suggests particularly weak and oscillatory euxinia, with an enhanced contribution of manganese (Mn) redox cycling to Mo deposition relative to the lower portion of the profile. This conclusion is supported by extreme sedimentary Mn enrichments of up to 15 weight percent. We interpret the combined data to indicate episodic but major Baltic inflow events of saline and oxygenated North Sea water into the anoxic Landsort Deep that limited the concentrations and residence time of water column sulfide and caused episodic oxide deposition. Considering the temporal overlap between the most reducing conditions and periods of redox instability, we hypothesize that major Baltic inflows, as is observed today, lead to short-term instability while simultaneously supporting longer-term Baltic anoxia by strengthening the halocline. Ultimately, our results indicate that periods more reducing than the modern Baltic Sea have occurred naturally over the Holocene, but the characteristic dynamic saline inputs have historically prevented the relatively more widespread and stable anoxia observed in other classic restricted basins and will likely continue to do so.

Depositional Conditions for the Kuna Formation, Red Dog Zn-Pb-Ag-Barite District, Alaska, Inferred from Isotopic and Chemical Proxies

Water column redox conditions, degree of restriction of the depositional basin, and other paleoenvironmental parameters have been determined for the Mississippian Kuna Formation of northwestern Alaska from stratigraphic profiles of Mo, Fe/Al, and S isotopes in pyrite, C isotopes in organic matter, and N isotopes in bulk rock. This unit is important because it hosts the Red Dog and Anarraaq Zn-Pb-Ag ± barite deposits, which together constitute one of the largest zinc resources in the world. The isotopic and chemical proxies record a deep basin environment that became isolated from the open ocean, became increasingly reducing, and ultimately became euxinic. The basin was ventilated briefly and then became isolated again just prior to its demise as a discrete depocenter with the transition to the overlying Siksikpuk Formation. Ventilation corresponded approximately to the initiation of bedded barite deposition in the district, whereas the demise of the basin corresponded approximately to the formation of the massive sulfide deposits. The changes in basin circulation during deposition of the upper Kuna Formation may have had multiple immediate causes, but the underlying driver was probably extensional tectonic activity that also facilitated fluid flow beneath the basin floor. Although the formation of sediment-hosted sulfide deposits is generally favored by highly reducing conditions, the Zn-Pb deposits of the Red Dog district are not found in the major euxinic facies of the Kuna basin, nor did they form during the main period of euxinia. Rather, the deposits occur where strata were permeable to migrating fluids and where excess H2S was available beyond what was produced in situ by decomposition of local sedimentary organic matter. The known deposits formed mainly by replacement of calcareous strata that gained H2S from nearby highly carbonaceous beds (Anarraaq deposit) or by fracturing and vein formation in strata that produced excess H2S by reductive dissolution of preexisting barite (Red Dog deposits).

The correlation between macroscopic algae and metazoans in the Ediacaran: a case study on the Wenghui biota in northeastern Guizhou, South China

After the Marinoan glaciation, macroscopic organisms thrived in the Yangtze Sea, South China, during the Ediacaran period. The Wenghui biota, which is found from the upper Doushantuo Formation black shales (>551 Ma) in northeastern Guizhou, South China, includes macroscopic algae, metazoans and ichnofossils. Most macroalgae in the Wenghui biota bear a holdfast to secure them onto seafloor and have a thallus of various lengths extending into the water column. This biota can be divided into Globusphyton, Sectoralga–Longifuniculum, Cucullus, Beltanelliformis and Baculiphyca–Gesinella assemblages. A fossil-barren interval containing a thin layer of feldspathic sandstone separates the macroscopic organisms into two distinct parts. From the Globusphyton assemblage through the Sectoralga–Longifuniculum assemblage to the Cucullus assemblage, metazoans show a positive correlation with the abundance and diversity of branching macroalgae at both metre and millimetre scales. Nevertheless, both Beltanelliformis and Baculiphyca–Gesinella assemblages, in which the number and diversity of macroscopic algae and metazoans, especially the shorter branching macroalgae, are obviously decreasing or even lacking, might be related to a special environment and a fragile ecosystem. In addition, the ratios of Ni/Co, U/Th and V/(V + Ni) display zigzagged profiles at millimetre scales indicating frequent redox fluctuations. Variations in macrofossils and trace elements at both millimetre and metre scales indicate that the oxygen content in the northeast Guizhou Sea fluctuated frequently during the middle–late Ediacaran period and the Wenghui biota possibly lived in the redox buffering zone. Moreover, the abundance and diversity of macroalgae, especially the branching macroalgae, could have significantly influenced the redox conditions in water column. The increase in oxygen may have improved the environment for the growth and reproduction of macroalgae and metazoans.

Assessing the utility of Fe/Al and Fe-speciation to record water column redox conditions in carbonate-rich sediments

Geochemical proxies based on Fe abundance (Fe/Al) and Fe-speciation have been widely applied to marine sediments in order to unravel paleo-depositional redox conditions though geological time. To date, however, these Fe proxies have only been calibrated in relation to modern and ancient fine-grained siliciclastic marine sediments. This clearly limits their use, particularly in relation to carbonate-rich sediments and rocks. To address this, we here explore the applicability of Fe-based redox proxies in carbonates through three approaches. First, we have compiled Fe/Al data for modern marine sediments to investigate variability in Fe-enrichments as a function of carbonate content and depositional setting. Second, we have expanded this approach with a compilation of new and existing Fe-speciation data for modern and ancient marine sediments deposited under oxic and euxinic (anoxic sulfidic) water column conditions. Finally, we show new data from paired limestone and dolomite sample sets to demonstrate the potential significance of deep burial dolomitization on the Fe-speciation redox proxy.Modern marine sediments deposited under oxic conditions show no relationship between Fe/Al and carbonate content. These sediments have an average Fe/Al ratio of 0.55±0.11, with some higher values potentially being attributable to steady-state early diagenetic remobilization of Fe towards the sediment–water interface. In contrast, significant Fe/Al enrichments occur as a consequence of water column Fe mineral formation and deposition, either under anoxic conditions, or due to input of anoxic hydrothermal fluids into oxic seawater. Iron speciation data also show no direct correlation with carbonate content, and instead three groups can be distinguished based on total Fe (FeT) and organic C contents. Sediments deposited under oxic water column conditions, with FeT >0.5wt.%, generally plot below the lower FeHR/FeT siliciclastic reference threshold (0.38) for distinguishing anoxic environments, regardless of carbonate content. Also consistent with siliciclastic calibrations, carbonate-rich sediments deposited under anoxic water column conditions tend to have FeHR/FeT ratios >0.38. In contrast, oxic carbonate-rich sediments with low FeT (<0.5wt.%) and low organic C (<0.5wt.%) routinely give spuriously high FeHR/FeT ratios, suggesting that the use of Fe-speciation for such samples is not appropriate for evaluating water column redox conditions. Taken together, our data suggest that an FeT content of >0.5wt.%, rather than carbonate content, represents the most suitable basis for identifying whether carbonate-rich sediments are appropriate for Fe-based redox proxy analyses. Analysis of burial dolostones suggests that the Fe-speciation proxy may also be compromised by deep burial dolomitization, where there has been a source of mobile Fe to enrich rocks during recrystallization. However, pre-screening can identify such samples. This new assessment expands the utility of Fe-based redox proxies to also incorporate appropriate carbonate-rich rocks, provided that care is taken to assess the possible impact of deep burial dolomitization.

Combining sedimentological, trace metal (Mn, Mo) and molecular evidence for reconstructing past water-column redox conditions: The example of meromictic Lake Cadagno (Swiss Alps)

Here, we present sedimentological, trace metal, and molecular evidence for tracking bottom water redox-state conditions during the past 12,500years in nowadays sulfidic and meromictic Lake Cadagno (Switzerland). A 10.5m long sediment core from the lake covering the Holocene period was investigated for concentration variations of the trace metals Mn and Mo (XRF core scanning and ICP-MS measurements), and for the presence of anoxygenic phototrophic sulfur bacteria (carotenoid pigment analysis and 16S rDNA real time PCR). Our trace metal analysis documents an oxic-intermediate-sulfidic redox-transition period beginning shortly after the lake formation ∼12.5kyr ago. The oxic period is characterized by low sedimentary Mn and Mo concentrations, as well as by the absence of any remnants of anoxygenic phototrophic sulfur bacteria. Enhanced accumulation/preservation of Mn (up to 5.6wt%) in the sediments indicates an intermediate, Mn-enriched oxygenation state with fluctuating redox conditions during a ∼2300-year long transition interval between ∼12.1 and 9.8kyr BP. We propose that the high Mn concentrations are the result of enhanced Mn2+ leaching from the sediments during reducing conditions and subsequent rapid precipitation of Mn-(oxyhydr)oxide minerals during episodic and short-term water-column mixing events mainly due to flood-induced underflows. At 9800±130calyr BP, a rapid transition to fully sulfidic conditions is indicated by the marked enrichment of Mo in the sediments (up to 490ppm), accompanied by an abrupt drop in Mn concentrations and the increase of molecular biomarkers that indicate the presence of anoxygenic photosynthetic bacteria in the water column. Persistently high Mo concentrations >80ppm provide evidence that sulfidic conditions prevailed thereafter until modern times, without any lasting hypolimnetic ventilation and reoxygenation. Hence, Lake Cadagno with its persistently stable chemocline offers a framework to study in great temporal detail over ∼12kyr the development of phototrophic sulfur bacteria communities and redox processes in a sulfidic environment, possibly depicting analogous conditions in an ancient ocean. Our study underscores the value of combining sedimentological, geochemical, and microbiological approaches to characterize paleo-environmental and -redox conditions in lacustrine and marine settings.