The Great Oxidation Event preceded a Paleoproterozoic "snowball Earth".

The inability to resolve the exact temporal relationship between two pivotal events in Earth history, the Paleoproterozoic Great Oxidation Event (GOE) and the first "snowball Earth" global glaciation, has precluded assessing causality between changing atmospheric composition and ancient climate change. Here we present temporally resolved quadruple sulfur isotope measurements (δ34S, ∆33S, and ∆36S) from the Paleoproterozoic Seidorechka and Polisarka Sedimentary Formations on the Fennoscandian Shield, northwest Russia, that address this issue. Sulfides in the former preserve evidence of mass-independent fractionation of sulfur isotopes (S-MIF) falling within uncertainty of the Archean reference array with a ∆36S/∆33S slope of -1.8 and have small negative ∆33S values, whereas in the latter mass-dependent fractionation of sulfur isotopes (S-MDF) is evident, with a ∆36S/∆33S slope of -8.8. These trends, combined with geochronological constraints, place the S-MIF/S-MDF transition, the key indicator of the GOE, between 2,501.5 ± 1.7 Ma and 2,434 ± 6.6 Ma. These are the tightest temporal and stratigraphic constraints yet for the S-MIF/S-MDF transition and show that its timing in Fennoscandia is consistent with the S-MIF/S-MDF transition in North America and South Africa. Further, the glacigenic part of the Polisarka Formation occurs 60 m above the sedimentary succession containing S-MDF signals. Hence, our findings confirm unambiguously that the S-MIF/S-MDF transition preceded the Paleoproterozoic snowball Earth. Resolution of this temporal relationship constrains cause-and-effect drivers of Earth's oxygenation, specifically ruling out conceptual models in which global glaciation precedes or causes the evolution of oxygenic photosynthesis.

Phosphate oxygen isotopic evidence for a temperate and biologically active Archaean ocean.

Oxygen and silicon isotope compositions of cherts and studies of protein evolution have been interpreted to reflect ocean temperatures of 55-85 degrees C during the early Palaeoarchaean era ( approximately 3.5 billion years ago). A recent study combining oxygen and hydrogen isotope compositions of cherts, however, makes a case for Archaean ocean temperatures being no greater than 40 degrees C (ref. 5). Ocean temperature can also be assessed using the oxygen isotope composition of phosphate. Recent studies show that (18)O:(16)O ratios of dissolved inorganic phosphate (delta(18)O(P)) reflect ambient seawater temperature as well as biological processing that dominates marine phosphorus cycling at low temperature. All forms of life require and concentrate phosphorus, and as a result of biological processing, modern marine phosphates have delta(18)O(P) values typically between 19-26 per thousand (VSMOW), highly evolved from presumed source values of approximately 6-8 per thousand that are characteristic of apatite in igneous rocks and meteorites. Here we report oxygen isotope compositions of phosphates in sediments from the 3.2-3.5-billion-year-old Barberton Greenstone Belt in South Africa. We find that delta(18)O(P) values range from 9.3 per thousand to 19.9 per thousand and include the highest values reported for Archaean rocks. The temperatures calculated from our highest delta(18)O(P) values and assuming equilibrium with sea water with delta(18)O = 0 per thousand (ref. 12) range from 26 degrees C to 35 degrees C. The higher delta(18)O(P) values are similar to those of modern marine phosphate and suggest a well-developed phosphorus cycle and evolved biologic activity on the Archaean Earth.

Increased barium levels in recent marine sediments from the Norwegian and Barents Seas suggest impact of hydrocarbon drilling and production.

Barium (Ba) in recent marine sediments can originate from natural and anthropogenic sources including discharges from the oil and gas industry. In this study, we use data from the Norwegian and Barents Seas to assess whether Ba in recent marine sediments has increased due to these discharges. To account for Ba in detrital material, we normalise all samples with respect to aluminosilicate by calculating an enrichment factor. We use statistical modelling to control for parameters related to sedimentation. We present results that suggest increased Ba levels in recent sediments that coincide with the timing of hydrocarbon drilling and production. This is supported by geographical differences on a large scale that relate to proximity to hydrocarbon drilling and production. Among 243 sampling stations, we identify 73 locations exhibiting enrichment of Ba in the upper 6 of sediment. At these locations, Ba is 1.55 to 3.55 times higher than the levels that can be expected from the shale average when Ba in detrital matter is accounted for. Excess Ba is reported in sediment surface samples in areas important to fisheries like the Lofoten area and the western Barents Sea.

Hydrothermal Regeneration of Ammonium as a Basin-Scale Driver of Primary Productivity.

Hydrothermal vents are important targets in the search for life on other planets due to their potential to generate key catalytic surfaces and organic compounds for biogenesis. Less well studied, however, is the role of hydrothermal circulation in maintaining a biosphere beyond its origin. In this study, we explored this question with analyses of organic carbon, nitrogen abundances, and isotopic ratios from the Paleoproterozoic Zaonega Formation (2.0 Ga), NW Russia, which is composed of interbedded sedimentary and mafic igneous rocks. Previous studies have documented mobilization of hydrocarbons, likely associated with magmatic intrusions into unconsolidated sediments. The igneous bodies are extensively hydrothermally altered. Our data reveal strong nitrogen enrichments of up to 0.6 wt % in these altered igneous rocks, suggesting that the hydrothermal fluids carried ammonium concentrations in the millimolar range, which is consistent with some modern hydrothermal vents. Furthermore, large isotopic offsets of ∼10‰ between organic-bound and silicate-bound nitrogen are most parsimoniously explained by partial biological uptake of ammonium from the vent fluid. Our results, therefore, show that hydrothermal activity in ancient marine basins could provide a locally high flux of recycled nitrogen. Hydrothermal nutrient recycling may thus be an important mechanism for maintaining a large biosphere on anoxic worlds.

New insights into submarine tailing disposal for a reduced environmental footprint: Lessons learnt from Norwegian fjords.

Submarine tailing disposal (STD) in fjords from land-based mines is common practice in Norway and takes place in other regions worldwide. We synthesize the results of a multidisciplinary programme on environmental impacts of STDs in Norwegian fjords, providing new knowledge that can be applied to assess and mitigate impact of tailing disposal globally, both for submarine and deep-sea activities. Detailed geological seafloor mapping provided data on natural sedimentation to monitor depositional processes on the seafloor. Modelling and analytical techniques were used to assess the behaviour of tailing particles and process-chemicals in the environment, providing novel tools for monitoring. Toxicity tests showed biological impacts on test species due to particulate and chemical exposure. Hypersedimentation mesocosm and field experiments showed a varying response on the benthos, allowing to determine the transition zone in the STD impact area. Recolonisation studies indicate that full community recovery and normalisation of metal leakage rates may take several decades due to bioturbation and slow burial of sulfidic tailings. The results are synthesised to provide guidelines for the development of best available techniques for STDs.

The kaolinite shuttle links the Great Oxidation and Lomagundi events.

The ~2.22-2.06 Ga Lomagundi Event was the longest positive carbon isotope excursion in Earth's history and is commonly interpreted to reflect perturbations in continental weathering and the phosphorous cycle. Previous models have focused on mechanisms of increasing phosphorous solubilization during weathering without focusing on transport to the oceans and its dispersion in seawater. Building from new experimental results, here we report kaolinite readily absorbs phosphorous under acidic freshwater conditions, but quantitatively releases phosphorous under seawater conditions where it becomes bioavailable to phytoplankton. The strong likelihood of high weathering intensities and associated high kaolinite content in post-Great-Oxidation-Event paleosols suggests there would have been enhanced phosphorus shuttling from the continents into marine environments. A kaolinite phosphorous shuttle introduces the potential for nonlinearity in the fluxes of phosphorous to the oceans with increases in chemical weathering intensity.

Monitoring the volume and lateral spread of disposed sediments by acoustic methods, Oslo Harbor, Norway.

Acoustic equipment, including interferometric sonar and parametric sub-bottom profiler, have been used to determine the volume and lateral spread of dredged sediments disposed in the natural submarine depression in the Bekkelag Basin, inner Oslofjord since the beginning of the Oslo Harbor remediation project in 2006. This natural depression is used as a subaqueous confined disposal facility (CDF). Calculation of the volume of disposed sediments in the CDF is based on elevation change, derived from two high-resolution bathymetric datasets obtained in 2004, i.e. before the onset of the remediation project, and in April 2008. Seismic profiles across the CDF have been used to estimate the settlement of the original seabed, caused by loading-induced dewatering and compaction of the seabed sediments under the disposed masses. Detailed bathymetry and backscatter data demonstrate the lateral spread of disposed sediments within a well-confined area covering ca. 195,000m(2). The sea bottom within this area is distinctly softer than the surrounding seabed as shown by very low acoustic backscatter amplitude, signifying a very loose surface character of the disposed sediments. The thickness of the disposed sediments reaches 6m the deepest part of the original depression. The volume calculation of the disposed sediments in the CDF, based solely on bathymetry data, gives a value of ca. 310,000-320,000m(3). Settlement of the original seabed as a result of loading has been estimated to be 30cm at 5m thickness of the disposed sediments. Under the condition that the settlement rate is linearly correlated to the thickness of disposed sediments, the settlement corrected volume of disposed sediments is ca. 330,000-340,000m(3). Presented results demonstrate high accuracy and good reproducibility of acoustic seafloor data, and indicate a great potential of such methods as monitoring tools in environmental projects that involve dredging and subaqueous disposal.

A 160,000-year-old history of tectonically controlled methane seepage in the Arctic.

The geological factors controlling gas release from Arctic deep-water gas reservoirs through seabed methane seeps are poorly constrained. This is partly due to limited data on the precise chronology of past methane emission episodes. Here, we use uranium-thorium dating of seep carbonates sampled from the seabed and from cores drilled at the Vestnesa Ridge, off West Svalbard (79°N, ~1200 m water depth). The carbonate ages reveal three emission episodes during the Penultimate Glacial Maximum (~160,000 to 133,000 years ago), during an interstadial in the last glacial (~50,000 to 40,000 years ago), and in the aftermath of the Last Glacial Maximum (~20,000 to 5,000 years ago), respectively. This chronology suggests that glacial tectonics induced by ice sheet fluctuations on Svalbard mainly controlled methane release from Vestnesa Ridge. Data corroborate past methane release in response to Northern Hemisphere cryosphere variations and suggest that Arctic deep-water gas reservoirs are sensitive to temperature variations over Quaternary time scales.

Image based quantitative comparisons indicate heightened megabenthos diversity and abundance at a site of weak hydrocarbon seepage in the southwestern Barents Sea.

BACKGROUND: High primary productivity in the midst of high toxicity defines hydrocarbon seeps; this feature usually results in significantly higher biomass, but in lower diversity communities at seeps rather than in the surrounding non-seep benthos. Qualitative estimates indicate that this dichotomy does not necessarily hold true in high latitude regions with respect to megafauna. Instead, high latitude seeps appear to function as local hotspots of both megafaunal diversity and abundance, although quantitative studies do not exist. In this study, we tested this hypothesis quantitatively by comparing georeferenced seafloor mosaics of a seep in the southwestern Barents Sea with the adjacent non-seep seafloor. METHODS: Seafloor images of the Svanefjell seep site and the adjacent non seep-influenced background seabed in the southwestern Barents Sea were used to construct georeferenced mosaics. All megafauna were enumerated and mapped on these mosaics and comparisons of the communities at the seep site and the non-seep background site were compared. Sediment push cores were taken in order to assess the sediment geochemical environment. RESULTS: Taxonomic richness and abundance were both considerably higher at the seep site than the non-seep location. However, taxa were fewer at the seep site compared to other seeps in the Barents Sea or the Arctic, which is likely due to the Svanefjell seep site exhibiting relatively low seepage rates (and correspondingly less chemosynthesis based primary production). Crusts of seep carbonates account for the higher diversity of the seep site compared to the background site, since most animals were either colonizing crust surfaces or using them for shelter or coverage. Our results indicate that seeps in northern latitudes can enhance local benthic diversity and this effect can take place even with weak seepage. Since crusts of seep carbonates account for most of the aggregating effect of sites experiencing moderate/weak seepage such as the study site, this means that the ability of seep sites to attract benthic species extends well beyond the life cycle of the seep itself, which has important implications for the larger marine ecosystem and its management policies.

Atypical biological features of a new cold seep site on the Lofoten-Vesterålen continental margin (northern Norway).

A newly discovered cold seep from the Lofoten-Vesterålen margin (Norwegian Sea) is dominated by the chemosymbiotrophic siboglinid Oligobrachia haakonmosbiensis like other high latitude seeps, but additionally displays uncharacteristic features. Sulphidic bottom water likely prevents colonization by cnidarians and sponges, resulting in fewer taxa than deeper seeps in the region, representing a deviation from depth-related trends seen among seeps elsewhere. O. haakonmosbiensis was present among carbonate and barite crusts, constituting the first record of frenulates among hard substrates. The presence of both adults and egg cases indicate that Ambylraja hyperborea skates use the site as an egg case nursery ground. Due to sub-zero ambient temperatures (-0.7 °C), we hypothesize that small, seepage related heat anomalies aid egg incubation and prevent embryo mortality. We place our results within the context of high-latitude seeps and suggest they exert evolutionary pressure on benthic species, thereby selecting for elevated exploitation and occupancy of high-productivity habitats.

Authigenesis of biomorphic apatite particles from Benguela upwelling zone sediments off Namibia: The role of organic matter in sedimentary apatite nucleation and growth.

Sedimentary phosphorites comprise a major phosphorus (P) ore, yet their formation remains poorly understood. Extant polyphosphate-metabolizing bacterial communities are known to act as bacterial phosphate-pumps, leading to episodically high dissolved phosphate concentrations in pore waters of organic-rich sediment. These conditions can promote the precipitation of amorphous precursor phases that are quickly converted to apatite-usually in carbonate fluorapatite form [Ca10 (PO4 ,CO3 )6 F2-3 ]. To assess the mechanisms underpinning the nucleation and growth of sedimentary apatite, we sampled P-rich sediments from the Namibian shelf, a modern environment where phosphogenesis presently occurs. The P-rich fraction of the topmost centimetres of sediment mainly consists of pellets about 50-400 µm in size, which in turn are comprised of micron-sized apatite particles that are often arranged into radial structures with diameters ranging from 2 to 4 µm, and morphologies that range from rod-shapes to dumbbells to spheres that resemble laboratory-grown fluorapatite-gelatin nanocomposites known from double-diffusion experiments in organic matrices. The nucleation and growth of authigenic apatite on the Namibian shelf is likely analogous to these laboratory-produced precipitates, where organic macromolecules play a central role in apatite nucleation and growth. The high density of apatite nucleation sites within the pellets (>109 particles per cm3 ) suggests precipitation at high pore water phosphate concentrations that have been reported from the Namibian shelf and may be attributed to microbial phosphate pumping. The intimate association of organic material with the apatite could suggest a possible role of biological substrata, such as exopolymeric substances (EPS), in the nucleation of apatite precursors. Importantly, we do not observe any evidence that the apatite particles are actual phosphatized microbes, contradicting some earlier studies. Nevertheless, these results further evidence the potential importance of microbially derived (extracellular) organic matter as a template for phosphatic mineral nucleation in both recent and ancient phosphorites.

Archean phosphorus liberation induced by iron redox geochemistry.

The element phosphorus (P) is central to ecosystem growth and is proposed to be a limiting nutrient for life. The Archean ocean may have been strongly phosphorus-limited due to the selective binding of phosphate to iron oxyhydroxide. Here we report a new route to solubilizing phosphorus in the ancient oceans: reduction of phosphate to phosphite by iron(II) at low (<200 °C) diagenetic temperatures. Reduction of phosphate to phosphite was likely widespread in the Archean, as the reaction occurs rapidly and is demonstrated from thermochemical modeling, experimental analogs, and detection of phosphite in early Archean rocks. We further demonstrate that the higher solubility of phosphite compared to phosphate results in the liberation of phosphorus from ferruginous sediments. This phosphite is relatively stable after its formation, allowing its accumulation in the early oceans. As such, phosphorus, not as phosphate but as phosphite, could have been a major nutrient in early pre-oxygenated oceans.

Timescales of methane seepage on the Norwegian margin following collapse of the Scandinavian Ice Sheet.

Gas hydrates stored on continental shelves are susceptible to dissociation triggered by environmental changes. Knowledge of the timescales of gas hydrate dissociation and subsequent methane release are critical in understanding the impact of marine gas hydrates on the ocean-atmosphere system. Here we report a methane efflux chronology from five sites, at depths of 220-400 m, in the southwest Barents and Norwegian seas where grounded ice sheets led to thickening of the gas hydrate stability zone during the last glaciation. The onset of methane release was coincident with deglaciation-induced pressure release and thinning of the hydrate stability zone. Methane efflux continued for 7-10 kyr, tracking hydrate stability changes controlled by relative sea-level rise, bottom water warming and fluid pathway evolution in response to changing stress fields. The protracted nature of seafloor methane emissions probably attenuated the impact of hydrate dissociation on the climate system.

Elevated levels of radium-226 and radium-228 in marine sediments of the Norwegian Trench ("Norskrenna") and Skagerrak.

Oil and gas extraction activities discharge waters bearing radium isotopes which may potentially be transported to locations distant from the discharge point. Sediment cores from the Norwegian Trench and Skagerrak, potential sinks for North Sea discharges, were analyzed for the contents of these isotopes. All cores were such that data could be obtained from periods prior to and during extensive operations in the North Sea. Results indicate elevated levels of radium isotopes in upper sedimentary layers when compared to data for the Baltic Sea and Kattegat. Although diagenetic processes involving manganese cycling may be responsible for these enrichments, the data support previous work indicating a possible influence of North Sea discharges on sediments of the area. The results highlight the need for further work on elaborating background levels of these isotopes in the North Sea and related areas such that possible impacts of these discharges can be properly evaluated.

Influence of historical industrial epochs on pore water and partitioning profiles of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in Oslo Harbor, Norway, sediment cores.

Contaminant levels in urban harbor sediments vary with contaminant emission levels, sedimentation rates, and sediment resuspension processes such as propeller wash. Levels of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are decreasing in many urban harbors, as heavily contaminated sediments that accumulated during past decades are being buried by less-contaminated sediments. However, PAHs and PCBs remain a concern in areas where burial is slow or resuspension processes re-expose heavily contaminated older layers. Chronostratigraphic sediment core studies typically characterize contaminant level histories by using total sediment concentrations, C(sed) , and do not determine the freely dissolved porewater concentrations, C(pw) , which provide a better measure of bioavailability. Here both C(sed) and C(pw) profiles were established for PAHs and PCBs in dated sediment cores from diverse areas of Oslo Harbor, Norway. Sediment-porewater partitioning profiles were established alongside profiles of various sorbing carbonaceous phases, including total organic carbon (TOC), black carbon, and diverse carbonaceous geosorbents identified by petrographic analysis. Stratigraphic trends in carbonaceous phases and C(sed) could be associated with different industrial epochs: hydropower (post-1960, approximately), manufactured gas (∼1925-1960), coal (∼1910-1925), and early industry (∼1860-1910). Partitioning was highly variable and correlated best with the TOC. Hydropower-epoch sediments exhibit decreasing C(sed) with time and a relatively strong sorption capacity compared with the manufactured-gas epoch. Sediments from the manufactured-gas epoch exhibit substantial PAH and metal contamination, large amounts of coke and char, and a low sorption capacity. Reexposure of sediments of this epoch increases risks to local benthic species. Implications on natural recovery as a sediment management strategy are discussed.

Isotopic evidence for massive oxidation of organic matter following the great oxidation event.

The stable isotope record of marine carbon indicates that the Proterozoic Eon began and ended with extreme fluctuations in the carbon cycle. In both the Paleoproterozoic [2500 to 1600 million years ago (Ma)] and Neoproterozoic (1000 to 542 Ma), extended intervals of anomalously high carbon isotope ratios (δ(13)C) indicate high rates of organic matter burial and release of oxygen to the atmosphere; in the Neoproterozoic, the high δ(13)C interval was punctuated by abrupt swings to low δ(13)C, indicating massive oxidation of organic matter. We report a Paleoproterozoic negative δ(13)C excursion that is similar in magnitude and apparent duration to the Neoproterozoic anomaly. This Shunga-Francevillian anomaly may reflect intense oxidative weathering of rocks as the result of the initial establishment of an oxygen-rich atmosphere.

Sedimentation and chronology of heavy metal pollution in Oslo harbor, Norway.

Stratigraphic profiles of Cu, Cd and Hg in ten sediment cores from the Oslo harbor, Norway, combined with results of radiometric dating demonstrate that pollution by these metals peaked between 1940 and 1970. Dating results indicate that Hg discharges peaked between 1940 and 1950, Cd reached maximum ca. 1955-1960, and Cu has the highest concentration in sediment interval corresponding to ca. 1970. Geochemical profiles and maxima of Cu, Cd and Hg concentrations can be used as chronostratigraphic markers for sediment cores from the Oslo harbor. Acoustic backscatter and sediment core data indicate that propeller wash affects the seabed in the Oslo harbor. The propeller-induced turbulence causes erosion, and in places exposes and remobilizes contaminated sediments that accumulated in the harbor during previous decades. Such re-exposure of contaminated sediments could be detrimental to local ecosystems and offset remediation efforts, warranting further impact studies and potential mitigation strategies to prevent redistribution.

Monitoring strategies for re-establishment of ecological reference conditions: possibilities and limitations.

The ecological status of an environment should be evaluated by comparison with local "reference conditions", here defined as the pre-industrial ecological status of the 19th century. This pilot study illustrates how micropalaeontological monitoring, using benthic foraminifera (protists) and associated geochemical parameters preserved in inner Oslofjord (Norway) sediments, characterise local reference conditions. In order to optimise the usefulness of the ecological information held by foraminifera and enable characterisation of temporal changes in environmental quality beyond time intervals covered by biological time-series, the Norwegian governmental macrofauna-based classification system is applied on fossil benthic foraminiferal assemblages. Quantitative comparisons demonstrate deteriorating ecological status in response to increased anthropogenic forcing (eutrophication, micropollutants), including a 73% loss in number of foraminiferal species. Despite reduced pollution during the past decades and, at one site, capping of polluted sediments with clean clay, the reference conditions are far from re-established. Micropalaeontological monitoring requires net sediment accumulation basins and careful considerations of taphonomic processes.

Reassessing the evidence for the earliest traces of life.

The isotopic composition of graphite is commonly used as a biomarker in the oldest (>3.5 Gyr ago) highly metamorphosed terrestrial rocks. Earlier studies on isotopic characteristics of graphite occurring in rocks of the approximately 3.8-Gyr-old Isua supracrustal belt (ISB) in southern West Greenland have suggested the presence of a vast microbial ecosystem in the early Archean. This interpretation, however, has to be approached with extreme care. Here we show that graphite occurs abundantly in secondary carbonate veins in the ISB that are formed at depth in the crust by injection of hot fluids reacting with older crustal rocks (metasomatism). During these reactions, graphite forms from the disproportionation of Fe(II)-bearing carbonates at high temperature. These metasomatic rocks, which clearly lack biological relevance, were earlier thought to be of sedimentary origin and their graphite association provided the basis for inferences about early life. The new observations thus call for a reassessment of previously presented evidence for ancient traces of life in the highly metamorphosed Early Archaean rock record.