What the ~1.4 Ga Xiamaling Formation can and cannot tell us about the mid‐Proterozoic ocean

Despite a surge of recent work, the evolution of mid‐Proterozoic oceanic–atmospheric redox remains heavily debated. Constraining the dynamics of Proterozoic redox evolution is essential to determine the role, if any, that anoxia played in protracting the development of eukaryotic diversity. We present a multiproxy suite of high‐resolution geochemical measurements from a drill core capturing the ~1.4 Ga Xiamaling Formation, North China Craton. Specifically, we analyzed major and trace element concentrations, sulfur and molybdenum isotopes, and iron speciation not only to better understand the local redox conditions but also to establish how relevant our data are to understanding the contemporaneous global ocean. Our results suggest that throughout deposition of the Xiamaling Formation, the basin experienced varying degrees of isolation from the global ocean. During deposition of the lower organic‐rich shales (130–85 m depth), the basin was extremely restricted, and the reservoirs of sulfate and trace metals were drawn down almost completely. Above a depth of 85 m, shales were deposited in dominantly euxinic waters that more closely resembled a marine system and thus potentially bear signatures of coeval seawater. In the most highly enriched sample from this upper interval, the concentration of molybdenum is 51 ppm with a δ⁹⁸Mo value of +1.7‰. Concentrations of Mo and other redox‐sensitive elements in our samples are consistent with a deep ocean that was largely anoxic on a global scale. Our maximum δ⁹⁸Mo value, in contrast, is high compared to published mid‐Proterozoic data. This high value raises the possibility that the Earth's surface environments were transiently more oxygenated at ~1.4 Ga compared to preceding or postdating times. More broadly, this study demonstrates the importance of integrating all available data when attempting to reconstruct surface O₂ dynamics based on rocks of any age.     

Microbial assemblage and palaeoenvironmental reconstruction of the 1.38 Ga Velkerri Formation,McArthur Basin,northern Australia

The ca. 1.38 billion years (Ga) old Roper Group of the McArthur Basin, northern Australia, is one of the most extensive Proterozoic hydrocarbon‐bearing units. Organic‐rich black siltstones from the Velkerri Formation were deposited in a deep‐water sequence and were analysed to determine their organic geochemical (biomarker) signatures, which were used to interpret the microbial diversity and palaeoenvironment of the Roper Seaway. The indigenous hydrocarbon biomarker assemblages describe a water column dominated by bacteria with large‐scale heterotrophic reworking of the organic matter in the water column or bottom sediment. Possible evidence for microbial reworking includes a large unresolved complex mixture (UCM), high ratios of mid‐chained and terminally branched monomethyl alkanes relative to n‐alkanes—features characteristic of indigenous Proterozoic bitumen. Steranes, biomarkers for single‐celled and multicellular eukaryotes, were below detection limits in all extracts analysed, despite eukaryotic microfossils having been previously identified in the Roper Group, albeit largely in organically lean shallower water facies. These data suggest that eukaryotes, while present in the Roper Seaway, were ecologically restricted and contributed little to export production. The 2,3,4‐ and 2,3,6‐trimethyl aryl isoprenoids (TMAI) were absent or in very low concentration in the Velkerri Formation. The low abundance is primary and not caused by thermal destruction. The combination of increased dibenzothiophene in the Amungee Member of the Velkerri Formation and trace metal redox geochemistry suggests that degradation of carotenoids occurred during intermittent oxygen exposure at the sediment–water interface and/or the water column was rarely euxinic in the photic zone and likely only transiently euxinic at depth. A comparison of this work with recently published biomarker and trace elemental studies from other mid‐Proterozoic basins demonstrates that microbial environments, water column geochemistry and basin redox were heterogeneous.     

Trace-element budgets in the Ohio/Sunbury shales of Kentucky: Constraints on ocean circulation and primary productivity in the Devonian–Mississippian Appalachian Basin

The hydrography of the Appalachian Basin in late Devonian–early Mississippian time is modeled based on the geochemistry of black shales and constrained by others' paleogeographic reconstructions. The model supports a robust exchange of basin bottom water with the open ocean, with residence times of less than forty years during deposition of the Cleveland Shale Member of the Ohio Shale. This is counter to previous interpretations of these carbon-rich units having accumulated under a stratified and stagnant water column, i.e., with a strongly restricted bottom bottom-water circulation. A robust circulation of bottom waters is further consistent with the palaeoclimatology, whereby eastern trade-winds drove upwelling and arid conditions limited terrestrial inputs of siliciclastic sediment, fresh waters, and riverine nutrients. The model suggests that primary productivity was high (~ 2 g C m^− 2 d^− 1), although no higher than in select locations in the ocean today. The flux of organic carbon settling through the water column and its deposition on the sea floor was similar to fluxes found in modern marine environments. Calculations based on the average accumulation rate of the marine fraction of Ni suggest the flux of organic carbon settling out of the water column was approximately 9% of primary productivity, versus an accumulation rate (burial) of organic carbon of 0.5% of primary productivity. Trace-element ratios of V:Mo and Cr:Mo in the marine sediment fraction indicate that bottom waters shifted from predominantly anoxic (sulfate reducing) during deposition of the Huron Shale Member of the Ohio Shale to predominantly suboxic (nitrate reducing) during deposition of the Cleveland Shale Member and the Sunbury Shale, but with anoxic conditions occurring intermittently throughout this period.     

Absence of biomarker evidence for early eukaryotic life from the Mesoproterozoic Roper Group: Searching across a marine redox gradient in mid‐Proterozoic habitability

By about 2.0 billion years ago (Ga), there is evidence for a period best known for its extended, apparent geochemical stability expressed famously in the carbonate–carbon isotope data. Despite the first appearance and early innovation among eukaryotic organisms, this period is also known for a rarity of eukaryotic fossils and an absence of organic biomarker fingerprints for those organisms, suggesting low diversity and relatively small populations compared to the Neoproterozoic era. Nevertheless, the search for diagnostic biomarkers has not been performed with guidance from paleoenvironmental redox constrains from inorganic geochemistry that should reveal the facies that were most likely hospitable to these organisms. Siltstones and shales obtained from drill core of the ca. 1.3–1.4 Ga Roper Group from the McArthur Basin of northern Australia provide one of our best windows into the mid‐Proterozoic redox landscape. The group is well dated and minimally metamorphosed (of oil window maturity), and previous geochemical data suggest a relatively strong connection to the open ocean compared to other mid‐Proterozoic records. Here, we present one of the first integrated investigations of Mesoproterozoic biomarker records performed in parallel with established inorganic redox proxy indicators. Results reveal a temporally variable paleoredox structure through the Velkerri Formation as gauged from iron mineral speciation and trace‐metal geochemistry, vacillating between oxic and anoxic. Our combined lipid biomarker and inorganic geochemical records indicate at least episodic euxinic conditions sustained predominantly below the photic zone during the deposition of organic‐rich shales found in the middle Velkerri Formation. The most striking result is an absence of eukaryotic steranes (4‐desmethylsteranes) and only traces of gammacerane in some samples—despite our search across oxic, as well as anoxic, facies that should favor eukaryotic habitability and in low maturity rocks that allow the preservation of biomarker alkanes. The dearth of Mesoproterozoic eukaryotic sterane biomarkers, even within the more oxic facies, is somewhat surprising but suggests that controls such as the long‐term nutrient balance and other environmental factors may have throttled the abundances and diversity of early eukaryotic life relative to bacteria within marine microbial communities. Given that molecular clocks predict that sterol synthesis evolved early in eukaryotic history, and (bacterial) fossil steroids have been found previously in 1.64 Ga rocks, then a very low environmental abundance of eukaryotes relative to bacteria is our preferred explanation for the lack of regular steranes and only traces of gammacerane in a few samples. It is also possible that early eukaryotes adapted to Mesoproterozoic marine environments did not make abundant steroid lipids or tetrahymanol in their cell membranes.     

A case study for late Archean and Proterozoic biogeochemical iron‐ and sulphur cycling in a modern habitat—the Arvadi Spring

As a consequence of Earth's surface oxygenation, ocean geochemistry changed from ferruginous (iron(II)‐rich) into more complex ferro‐euxinic (iron(II)‐sulphide‐rich) conditions during the Paleoproterozoic. This transition must have had profound implications for the Proterozoic microbial community that existed within the ocean water and bottom sediment; in particular, iron‐oxidizing bacteria likely had to compete with emerging sulphur‐metabolizers. However, the nature of their coexistence and interaction remains speculative. Here, we present geochemical and microbiological data from the Arvadi Spring in the eastern Swiss Alps, a modern model habitat for ferro‐euxinic transition zones in late Archean and Proterozoic oceans during high‐oxygen intervals, which enables us to reconstruct the microbial community structure in respective settings for this geological era. The spring water is oxygen‐saturated but still contains relatively elevated concentrations of dissolved iron(II) (17.2 ± 2.8 μM) and sulphide (2.5 ± 0.2 μM) with simultaneously high concentrations of sulphate (8.3 ± 0.04 mM). Solids consisting of quartz, calcite, dolomite and iron(III) oxyhydroxide minerals as well as sulphur‐containing particles, presumably elemental S⁰, cover the spring sediment. Cultivation‐based most probable number counts revealed microaerophilic iron(II)‐oxidizers and sulphide‐oxidizers to represent the largest fraction of iron‐ and sulphur‐metabolizers in the spring, coexisting with less abundant iron(III)‐reducers, sulphate‐reducers and phototrophic and nitrate‐reducing iron(II)‐oxidizers. 16S rRNA gene 454 pyrosequencing showed sulphide‐oxidizing Thiothrix species to be the dominating genus, supporting the results from our cultivation‐based assessment. Collectively, our results suggest that anaerobic and microaerophilic iron‐ and sulphur‐metabolizers could have coexisted in oxygenated ferro‐sulphidic transition zones of late Archean and Proterozoic oceans, where they would have sustained continuous cycling of iron and sulphur compounds.     

Associations between redox‐sensitive trace metals and microbial communities in a Proterozoic ocean analogue

Constraints on Precambrian ocean chemistry are dependent upon sediment geochemistry. However, diagenesis and metamorphism can destroy primary biosignatures, making it difficult to consider biology when interpreting geochemical data. Modern analogues for ancient ecosystems can be useful tools for identifying how sediment geochemistry records an active biosphere. The Middle Island Sinkhole (MIS) in Lake Huron is an analogue for shallow Proterozoic waters due to its low oxygen water chemistry and microbial communities that exhibit diverse metabolic functions at the sediment–water interface. This study uses sediment trace metal contents and microbial abundances in MIS sediments and an oxygenated Lake Huron control site (LH) to infer mechanisms for trace metal burial. The adsorption of trace metals to Mn‐oxyhydroxides is a critical burial pathway for metals in oxic LH sediments, but not for the MIS mat and sediments, consistent with conventional understanding of Mn cycling. Micronutrient trace metals (e.g., Zn) are associated with organic matter regardless of oxygen and sulfide availability. Although U and V are conventionally considered to be organically complexed in suboxic and anoxic conditions, U and organic covary in oxic LH sediments, and Mn‐oxyhydroxide cycling dominates V deposition in the anoxic MIS sediments. Significant correlations between Mo and organic matter across all redox regimes have major implications for our interpretations of Mo isotope systematics in the geologic record. Finally, while microbial groups vary between the sampling locales (e.g., the cyanobacteria in the MIS microbial mat are not present in LH sediments), LH and MIS ultimately have similar relationships between microbial assemblages and metal burial, making it difficult to link trace metal burial to microbial metabolisms. Together, these results indicate that bulk sediment trace metal composition does not capture microbiological processes; more robust trace metal geochemistry such as isotopes and speciation may be critical for understanding the intersections between microbiology and sediment geochemistry.     

Fine‐scale vertical and horizontal movements of juvenile yellowfin tuna (Thunnus albacares) associated with a subsurface fish aggregating device (FAD) off southwestern Taiwan

An increase in yellowfin tuna (Thunnus albacares) catch by danish seine fisheries around the subsurface fish aggregating devices (FADs) in southern Taiwan waters has been a concern of local government and environmental groups. However, the attraction mechanism of aggregating tunas at the subsurface FADs is still poorly understood. The objective of this study is to examine the fine‐scale vertical and horizontal movements of juvenile yellowfin tunas around a subsurface FAD. In total, 53 tunas (35–81 cm fork length) were tagged with ultrasonic telemetry tags and released at a subsurface FAD in the waters off Shiao‐Liu‐Chiu Island, southwestern Taiwan from October 2008 to December 2009. These tunas stayed at the subsurface FAD for up to 31 days, with daytime vertical movement depths averaging 60–80 m at a maximum depth of 250 m. At night, the tuna gathered at a shallow depth of 40 m. The mean depth of vertical movement in the daytime is significantly different from that of the nighttime (P < 0.05). The maximum detectable distance of horizontal movement was 1.6 km, with 80% of the long horizontal movements occurring in the daytime. It is likely that the purpose of these vertical and horizontal movements was for feeding or avoiding predators. Moreover, the tagged tunas did not depart from the subsurface FAD simultaneously, suggesting distinct behaviors in their movements.     

Paleoecology and paleoceanography of the Athel silicilyte,Ediacaran–Cambrian boundary,Sultanate of Oman

The Athel silicilyte is an enigmatic, hundreds of meters thick, finely laminated quartz deposit, in which silica precipitated in deep water (>~100–200 m) at the Ediacaran–Cambrian boundary in the South Oman Salt Basin. In contrast, Meso‐Neoproterozoic sinks for marine silica were dominantly restricted to peritidal settings. The silicilyte is known to contain sterane biomarkers for demosponges, which today are benthic, obligately aerobic organisms. However, the basin has previously been described as permanently sulfidic and time‐equivalent shallow‐water carbonate platform and evaporitic facies lack silica. The Athel silicilyte thus represents a unique and poorly understood depositional system with implications for late Ediacaran marine chemistry and paleoecology. To address these issues, we made petrographic observations, analyzed biomarkers in the solvent‐extractable bitumen, and measured whole‐rock iron speciation and oxygen and silicon isotopes. These data indicate that the silicilyte is a distinct rock type both in its sedimentology and geochemistry and in the original biology present as compared to other facies from the same time period in Oman. The depositional environment of the silicilyte, as compared to the bounding shales, appears to have been more reducing at depth in sediments and possibly bottom waters with a significantly different biological community contributing to the preserved biomarkers. We propose a conceptual model for this system in which deeper, nutrient‐rich waters mixed with surface seawater via episodic mixing, which stimulated primary production. The silica nucleated on this organic matter and then sank to the seafloor, forming the silicilyte in a sediment‐starved system. We propose that the silicilyte may represent a type of environment that existed elsewhere during the Neoproterozoic. These environments may have represented an important locus for silica removal from the oceans.     

Constraining oceanic oxygenation during the Shuram excursion in South China using thallium isotopes

Ediacaran sediments record an unusual global carbon cycle perturbation that has been linked to widespread oceanic oxygenation, the Shuram negative C isotope excursion (NCIE). However, proxy‐based estimates of global ocean redox conditions during this event have been limited largely due to proxy specificity (e.g., euxinic sediments for Mo and U isotopes). Modern global seawater documents a homogenous Tl isotope composition (ε²⁰⁵Tl = ?6.0) due to significant manganese oxide burial, which is recorded in modern euxinic sediments. Here, we provide new data documenting that sediments deposited beneath reducing but a non‐sulfidic water column from the Santa Barbara Basin (ε²⁰⁵Tl = ?5.6 ± 0.1) also faithfully capture global seawater Tl isotope values. Thus, the proxy utilization of Tl isotopes can extend beyond strictly euxinic settings. Second, to better constrain the global redox conditions during the Shuram NCIE, we measured Tl isotopes of locally euxinic and ferruginous shales of the upper Doushantuo Formation, South China. The ε²⁰⁵Tl values of these shales exhibit a decreasing trend from ≈?3 to ≈?8, broadly coinciding with the onset of Shuram NCIE. There are ε²⁰⁵Tl values (?5.1 to ?7.8) during the main Shuram NCIE interval that approach values more negative than modern global seawater. These results suggest that manganese oxide burial was near or even greater than modern burial fluxes, which is likely linked to an expansion of oxic conditions. This ocean oxygenation may have been an important trigger for the Shuram NCIE and evolution of Ediacaran‐type biota. Subsequently, Tl isotopes show an increasing trend from the modern ocean value to values near the modern global inputs or even heavier (ε²⁰⁵Tl ≈ ?2.5 ~ 0.4), occurring prior to recovery from the NCIE. These records may suggest that there was a decrease in the extent of oxygenated conditions in the global oceans during the late stage of the Shuram NCIE.     

Metal limitation of cyanobacterial N2 fixation and implications for the Precambrian nitrogen cycle

Nitrogen fixation is a critical part of the global nitrogen cycle, replacing biologically available reduced nitrogen lost by denitrification. The redox‐sensitive trace metals Fe and Mo are key components of the primary nitrogenase enzyme used by cyanobacteria (and other prokaryotes) to fix atmospheric N₂ into bioessential compounds. Progressive oxygenation of the Earth's atmosphere has forced changes in the redox state of the oceans through geologic time, from anoxic Fe‐enriched waters in the Archean to partially sulfidic deep waters by the mid‐Proterozoic. This development of ocean redox chemistry during the Precambrian led to fluctuations in Fe and Mo availability that could have significantly impacted the ability of prokaryotes to fix nitrogen. It has been suggested that metal limitation of nitrogen fixation and nitrate assimilation, along with increased rates of denitrification, could have resulted in globally reduced rates of primary production and nitrogen‐starved oceans through much of the Proterozoic. To test the first part of this hypothesis, we grew N₂‐fixing cyanobacteria in cultures with metal concentrations reflecting an anoxic Archean ocean (high Fe, low Mo), a sulfidic Proterozoic ocean (low Fe, moderate Mo), and an oxic Phanerozoic ocean (low Fe, high Mo). We measured low rates of cellular N₂ fixation under [Fe] and [Mo] estimated for the Archean ocean. With decreased [Fe] and higher [Mo] representing sulfidic Proterozoic conditions, N₂ fixation, growth, and biomass C:N were similar to those observed with metal concentrations of the fully oxygenated oceans that likely developed in the Phanerozoic. Our results raise the possibility that an initial rise in atmospheric oxygen could actually have enhanced nitrogen fixation rates to near modern marine levels, providing that phosphate was available and rising O₂ levels did not markedly inhibit nitrogenase activity.     

Microbes,mud and methane: cause and consequence of recurrent Early Jurassic anoxia following the end‐Triassic mass extinction

The end‐Triassic mass extinction (c. 201.6 Ma) was one of the five largest mass‐extinction events in the history of animal life. It was also associated with a dramatic, long‐lasting change in sedimentation style along the margins of the Tethys Ocean, from generally organic‐matter‐poor sediments during the Triassic to generally organic‐matter‐rich black shales during the Jurassic. New core material from Germany provides biomarker evidence of persistent photic‐zone euxinia during the Hettangian, the onset of which is associated with a series of both negative and positive carbon isotope excursions. Combined inorganic and organic geochemical and micropalaeontological analyses reveal strong similarities between the Hettangian and the better‐known Toarcian anoxic event. These events appear to be the most clearly expressed events within a series of anoxic episodes that also include poorly studied black shale intervals during the Sinemurian and Pliensbachian. Both the Hettangian and Toarcian events are marked by important changes in phytoplankton assemblages from chromophyte‐ to chlorophyte‐dominated assemblages within the European Epicontinental Seaway. Phytoplankton changes occurred in association with the establishment of photic‐zone euxinia, driven by a general increase in salinity stratification and warming of surface waters. For both events, the causes of large negative carbon isotope excursions remain incompletely understood; evidence exists for both variation in the δ¹³C of atmospheric CO₂ and variation in the sources of organic carbon. Regardless of the causes of δ¹³C variability, long‐term ocean anoxia during the Early Jurassic can be attributed to greenhouse warming and increased nutrient delivery to the oceans triggered by flood basalt volcanism.     

Land‐use legacy and the differential response of stream macroinvertebrates to multiple stressors studied using in situ experimental mesocosms

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Microbially influenced formation of Neoarchean ooids

Ooids are accretionary grains commonly reported from turbulent, shallow‐water environments. They have long been associated with microbially dominated ecosystems and often occur in close proximity to, or embedded within, stromatolites, yet have historically been thought to form solely through physicochemical processes. Numerous studies have revealed both constructive and destructive roles for microbes colonizing the surfaces of modern calcitic and aragonitic ooids, but there has been little evidence for the operation of these processes during the Archean and Proterozoic, when both ooids and microbially dominated ecosystems were more widespread. Recently described carbonate ooids from the 2.9 Ga Pongola Supergroup, South Africa, include well‐preserved examples composed of diagenetic dolomite interpreted to have formed from a high‐Mg‐calcite precursor. Spatial distributions of organic matter and elements associated with metabolic activity (N, S, and P) were interpreted as evidence for a biologically induced origin. Here, we describe exceptionally well‐preserved ooids composed of calcite, collected from Earth's oldest known carbonate lake system, the ~2.72 Ga Meentheena Member (Tumbiana Formation), Fortescue Group, Western Australia. We used optical microscopy, Raman spectroscopy, XRD, SEM‐EDS, LA‐ICP‐MS, EA‐IRMS, and a novel micro‐XRF instrument to investigate an oolite shoal deposited between stromatolites that preserve abundant evidence for microbial activity. We report an extremely fine, radial‐concentric, calcitic microfabric that is similar to the primary and early diagenetic fabrics of calcitic ooids reported from modern temperate lakes. Early diagenetic silica has trapped isotopically light and thermally mature organic matter. The close association of organic matter with mineral phases and microfabrics related to primary and early diagenetic processes suggest incorporation of organic matter occurred during accretion, likely due to the presence of microbial biofilms. We conclude that the oldest known calcitic ooids were likely formed through processes similar to those that mediate the accretion of ooids in similar environments today, including formation within a microbial biosphere.     

Modeling the carbon cycle in Lake Matano

Lake Matano, Indonesia, is a stratified anoxic lake with iron‐rich waters that has been used as an analogue for the Archean and early Proterozoic oceans. Past studies of Lake Matano report large amounts of methane production, with as much as 80% of primary production degraded via methanogenesis. Low δ¹³C values of DIC in the lake are difficult to reconcile with this notion, as fractionation during methanogenesis produces isotopically heavy CO₂. To help reconcile these observations, we develop a box model of the carbon cycle in ferruginous Lake Matano, Indonesia, that satisfies the constraints of CH₄ and DIC isotopic profiles, sediment composition, and alkalinity. We estimate methane fluxes smaller than originally proposed, with about 9% of organic carbon export to the deep waters degraded via methanogenesis. In addition, despite the abundance of Fe within the waters, anoxic ferric iron respiration of organic matter degrades <3% of organic carbon export, leaving methanogenesis as the largest contributor to anaerobic organic matter remineralization, while indicating a relatively minor role for iron as an electron acceptor. As the majority of carbon exported is buried in the sediments, we suggest that the role of methane in the Archean and early Proterozoic oceans is less significant than presumed in other studies.     

Storage and release of solutes from a subalpine seasonal snowpack: soil and stream water response, Niwot Ridge, Colorado

Much of the research on the chemistry of snow and surface waters of the western US, Europe, and Asia has been conducted in high-elevation catchments above treeline. Here we provide information on the solute content of the seasonal snowpack at the Soddie site on Niwot Ridge, Colorado, a subalpine site near treeline. We focus on the storage and release of both inorganic and organic solutes to the soils underneath the snowpack, and subsequent effects on the chemical and nutrient content of the underlying soil solution and the adjacent headwater stream. The concentration of inorganic nitrogen (N) stored in the seasonal snowpack at the Soddie site of about 11 μeq L⁻¹ was on the upper end of values reported for the northern hemisphere when compared to most areas of the Alps, Himalayas, and Tien Shan mountain ranges, but consistent with other reports of snowpacks in the Rocky Mountains. The storage of inorganic N in the snowpack at maximum accumulation averaged about 17 meq m⁻², or 170 eq ha⁻¹ (on the order of 2 kg-N ha⁻¹). Solutes were released from storage in the form of an ionic pulse, with a maximum concentration factor of about four. In contrast to the seasonal snowpack, the dominant form of N in the soil solution was dissolved organic N. Thus, soils underlying the seasonal snowpack appear to assimilate inorganic N released from storage in the snowpack and convert it to organic N. A two component mixing model suggests that the majority of streamflow was this year’s snowmelt that had infiltrated the subsurface and undergone subsequent biological and geochemical reactions. The inorganic N in surface waters at the headwaters of Como creek were always near or below detection limits, suggesting that this area at treeline is still N-limited.     

Effect of ice melting on bacterial carbon fluxes channelled by viruses and protists in the Arctic Ocean

During the last few years, extensive sea ice melting in the Arctic due to climate change has been detected, which could potentially modify the organic carbon fluxes in these waters. In this study, the effect of sea ice melting on bacterial carbon channelling by phages and protists has been evaluated in the northern Greenland Sea and Arctic Ocean. Grazing on bacteria by protists was evaluated using the FLB disappearance method. Lysis of bacteria due to viral infections was measured using the virus reduction approach. Losses of bacterial production caused by protists (PMM_BP) dominated losses caused by viruses (VMM_BP) throughout the study. Lysogenic viral production was detected in 7 out of 21 measurements and constituted from 33.9 to 100.0% of the total viral production. Significantly higher PMM_BP and lower VMM_BP were detected in waters affected by ice melting compared with unaffected waters. Consequently, significantly more bacterial carbon was channelled to the higher trophic levels in affected waters (13.05 ± 5.98 μgC l⁻¹ day⁻¹) than in unaffected waters (8.91 ± 8.33 μgC l⁻¹ day⁻¹). Viruses channelled 2.63 ± 2.45 μgC l⁻¹ day⁻¹ in affected waters and 4.27 ± 5.54 μgC l⁻¹ day⁻¹ in unaffected waters. We conclude that sea ice melting in the Arctic could modify the carbon flow through the microbial food web. This process may be especially important in the case of massive sea ice melting due to climate change.     

Discovery of the oldest known biomarkers provides evidence for phototrophic bacteria in the 1.73 Ga Wollogorang Formation,Australia

The discovery of mid‐Proterozoic (1.8–0.8 billion years ago, Ga) indigenous biomarkers is a challenge, since biologically informative molecules of such antiquity are commonly destroyed by metamorphism or overprinted by drilling fluids and other anthropogenic petroleum products. Previously, the oldest clearly indigenous biomarkers were reported from the 1.64 Ga Barney Creek Formation in the northern Australian McArthur Basin. In this study, we present the discovery of biomarker molecules from carbonaceous shales of the 1.73 Ga Wollogorang Formation in the southern McArthur Basin, extending the biomarker record back in time by ~90 million years. The extracted hydrocarbons illustrate typical mid‐Proterozoic signatures with a large unresolved complex mixture, high methyl alkane/n‐alkane ratios and the absence of eukaryotic steranes. Acyclic isoprenoids, saturated carotenoid derivatives, bacterial hopanes and aromatic hopanoids and steroids also were below detection limits. However, continuous homologous series of low molecular weight C₁₄–C₁₉ 2,3,4‐ and 2,3,6‐trimethyl aryl isoprenoids (AI) were identified, and C₂₀–C₂₂ AI homologues were tentatively identified. Based on elevated abundances relative to abiogenic isomers, we interpret the 2,3,6‐AI isomer series as biogenic molecules and the 2,3,4‐AI series as possibly biogenic. The biological sources for the 2,3,6‐AI series include carotenoids of cyanobacteria and/or green sulphur bacteria (Chlorobiaceae). The lower concentrated 2,3,4‐AI series may be derived from purple sulphur bacteria (Chromatiaceae). These degradation products of carotenoids are the oldest known clearly indigenous molecules of likely biogenic origin.     

Carbon pump dynamics and limited organic carbon burial during OAE1a

Oceanic Anoxic Events (OAEs) are conspicuous intervals in the geologic record that are associated with the deposition of organic carbon (OC)-rich marine sediment, linked to extreme biogeochemical perturbations, and characterized by widespread ocean deoxygenation. Mechanistic links between the marine biological carbon pump (BCP), redox conditions, and organic carbon burial during OAEs, however, remain poorly constrained. In this work we reconstructed the BCP in the western Tethys Ocean across OAE1a (~120 Mya) using sediment geochemistry and OC mass accumulation rates (OC_Acc). We find that OC_Acc were between 0.006 and 3.3 gC m⁻² yr⁻¹, with a mean value of 0.79 ± 0.78 SD gC m⁻² yr⁻¹—these rates are low and comparable to oligotrophic regions in the modern oceans. This challenges longstanding assumptions that oceanic anoxic events are intervals of strongly elevated organic carbon burial. Numerical modelling of the BCP, furthermore, reveals that such low OC fluxes are only possible with either or both low to moderate OC export fluxes from ocean surface waters, with rates similar to oligotrophic (nutrient-poor, <30 gC m⁻² yr⁻¹) and mesotrophic (moderate-nutrients, ~50–100 gC m⁻² yr⁻¹) regions in the modern ocean, and stronger than modern vertical OC attenuation. The low OC fluxes thus reflect a relatively weak BCP. Low to moderate productivity is further supported by palaeoecological and geochemical evidence and was likely maintained through nutrient limitation that developed in response to the burial and sequestration of phosphorus in association with iron minerals under ferruginous (anoxic iron-rich) ocean conditions. Without persistently high productivity, ocean deoxygenation during OAE1a was more likely driven by other physicochemical and biological factors including ocean warming, changes in marine primary producer community composition, and fundamental shifts in the efficiency of the BCP with associated effects and feedbacks.     

Sensitivity of soil carbon fractions and their specific stabilization mechanisms to extreme soil warming in a subarctic grassland

Terrestrial carbon cycle feedbacks to global warming are major uncertainties in climate models. For in‐depth understanding of changes in soil organic carbon (SOC) after soil warming, long‐term responses of SOC stabilization mechanisms such as aggregation, organo‐mineral interactions and chemical recalcitrance need to be addressed. This study investigated the effect of 6 years of geothermal soil warming on different SOC fractions in an unmanaged grassland in Iceland. Along an extreme warming gradient of +0 to ~+40 °C, we isolated five fractions of SOC that varied conceptually in turnover rate from active to passive in the following order: particulate organic matter (POM), dissolved organic carbon (DOC), SOC in sand and stable aggregates (SA), SOC in silt and clay (SC‐rSOC) and resistant SOC (rSOC). Soil warming of 0.6 °C increased bulk SOC by 22 ± 43% (0–10 cm soil layer) and 27 ± 54% (20–30 cm), while further warming led to exponential SOC depletion of up to 79 ± 14% (0–10 cm) and 74 ± 8% (20–30) in the most warmed plots (~+40 °C). Only the SA fraction was more sensitive than the bulk soil, with 93 ± 6% (0–10 cm) and 86 ± 13% (20–30 cm) SOC losses and the highest relative enrichment in ¹³C as an indicator for the degree of decomposition (+1.6 ± 1.5‰ in 0–10 cm and +1.3 ± 0.8‰ in 20–30 cm). The SA fraction mass also declined along the warming gradient, while the SC fraction mass increased. This was explained by deactivation of aggregate‐binding mechanisms. There was no difference between the responses of SC‐rSOC (slow‐cycling) and rSOC (passive) to warming, and ¹³C enrichment in rSOC was equal to that in bulk soil. We concluded that the sensitivity of SOC to warming was not a function of age or chemical recalcitrance, but triggered by changes in biophysical stabilization mechanisms, such as aggregation.     

Global change effects on the long‐term feeding ecology and contaminant exposures of East Greenland polar bears

Rapid climate changes are occurring in the Arctic, with substantial repercussions for arctic ecosystems. It is challenging to assess ecosystem changes in remote polar environments, but one successful approach has entailed monitoring the diets of upper trophic level consumers. Quantitative fatty acid signature analysis (QFASA) and fatty acid carbon isotope (δ¹³C‐FA) patterns were used to assess diets of East Greenland (EG) polar bears (Ursus maritimus) (n = 310) over the past three decades. QFASA‐generated diet estimates indicated that, on average, EG bears mainly consumed arctic ringed seals (47.5 ± 2.1%), migratory subarctic harp (30.6 ± 1.5%) and hooded (16.7 ± 1.3%) seals and rarely, if ever, consumed bearded seals, narwhals or walruses. Ringed seal consumption declined by 14%/decade over 28 years (90.1 ± 2.5% in 1984 to 33.9 ± 11.1% in 2011). Hooded seal consumption increased by 9.5%/decade (0.0 ± 0.0% in 1984 to 25.9 ± 9.1% in 2011). This increase may include harp seal, since hooded and harp seal FA signatures were not as well differentiated relative to other prey species. Declining δ¹³C‐FA ratios supported shifts from more nearshore/benthic/ice‐associated prey to more offshore/pelagic/open‐water‐associated prey, consistent with diet estimates. Increased hooded seal and decreased ringed seal consumption occurred during years when the North Atlantic Oscillation (NAO) was lower. Thus, periods with warmer temperatures and less sea ice were associated with more subarctic and less arctic seal species consumption. These changes in the relative abundance, accessibility, or distribution of arctic and subarctic marine mammals may have health consequences for EG polar bears. For example, the diet change resulted in consistently slower temporal declines in adipose levels of legacy persistent organic pollutants, as the subarctic seals have higher contaminant burdens than arctic seals. Overall, considerable changes are occurring in the EG marine ecosystem, with consequences for contaminant dynamics.