Coupled Mo-U abundances and isotopes in a small marine euxinic basin: constraints on processes in euxinic basins

Sedimentary molybdenum (Mo) and uranium (U) abundances, as well as their isotope systematics, are used to reconstruct the evolution of the oxygenation state of the surface Earth from the geological record. Their utility in this endeavour must be underpinned by a thorough understanding of their behaviour in modern settings. In this study, Mo-U concentrations and their isotope compositions were measured in the water column, sinking particles, sediments and pore waters of the marine euxinic Lake Rogoznica (Adriatic Sea, Croatia) over a two year period, with the aim of shedding light on the specific processes that control Mo-U accumulation and isotope fractionations in anoxic sediment. Lake Rogoznica is a 15 m deep stratified sea-lake that is anoxic and euxinic at depth. The deep euxinic part of the lake generally shows Mo depletions consistent with near-quantitative Mo removal and uptake into sediments, with Mo isotope compositions close to the oceanic composition. The data also, however, show evidence for periodic additions of isotopically light Mo to the lake waters, possibly released from authigenic precipitates formed in the upper oxic layer and subsequently processed through the euxinic layer. The data also show evidence for a small isotopic offset (~0.3‰ on 98Mo/95Mo) between particulate and dissolved Mo, even at highest sulfide concentrations, suggesting minor Mo isotope fractionation during uptake into euxinic sediments. Uranium concentrations decrease towards the bottom of the lake, where it also becomes isotopically lighter. The U systematics in the lake show clear evidence for a dominant U removal mechanism via diffusion into, and precipitation in, euxinic sediments, though the diffusion profile is mixed away under conditions of increased density stratification between an upper oxic and lower anoxic layer. The U diffusion-driven precipitation is best described with an effective 238U/235U fractionation of +0.6‰, in line with other studied euxinic basins. Combining the Mo and U systematics in Lake Rogoznica and other euxinic basins, it is apparent that the two different uptake mechanisms of U and Mo can lead to spatially and temporally variable Mo/U and Mo-U isotope systematics that depend on the rate of water renewal versus removal to sediment, the sulfide concentration, and the geometry of the basin. This study further emphasises the potential of combining multiple observations, from Mo-U enrichment and isotope systematics, for disentangling the various processes via which redox conditions control the chemistry of modern and ancient sediments

Biogeochemical Dynamics of Molybdenum in a Crater Lake: Seasonal Impact and Long-Term Removal

International audienceDespite a large variety of processes that can control Mo and its potential to become an environmental tracer of euxinic environment, this element is not often studied in lakes. The aim of this paper is to identify main seasonal biogeochemical processes that involve Mo in a well constrained freshwater system (Lake Pavin water-column) in order to evaluate their respective importance. In Lake Pavin, 4 main processes have been identified: 1) the transitional process represented by Mo assimilation of by phytoplankton in the epilimnion (nitrogen biological fixation and nitrate assimilation); 2) transient process represented by dissolved Mo adsorption onto Fe and Mn metal oxides at oxic/anoxic interface (depth 50 - 60 m); 3) Mo precipitation where apparent sulfide production rate is maximum, and from 80 m depths; 4) release of dissolved Mo due to Mo benthic flux or input from a deep source

Phototrophic Fe(II)-oxidation in the chemocline of a ferruginous meromictic lake

© 2014 Walter, Picazo, Miracle, Vicente, Camacho, Aragno and Zopfi. Precambrian Banded Iron Formation (BIF) deposition was conventionally attributed to the precipitation of iron-oxides resulting from the abiotic reaction of ferrous iron (Fe(II)) with photosynthetically produced oxygen. Earliest traces of oxygen date from 2.7 Ga, thus raising questions as to what may have caused BIF precipitation before oxygenic photosynthesis evolved. The discovery of anoxygenic phototrophic bacteria thriving through the oxidation of Fe(II) has provided support for a biological origin for some BIFs, but despite reports suggesting that anoxygenic phototrophs may oxidize Fe(II) in the environment, a model ecosystem of an ancient ocean where they are demonstrably active was lacking. Here we show that anoxygenic phototrophic bacteria contribute to Fe(II) oxidation in the water column of the ferruginous sulfate-poor, meromictic lake La Cruz (Spain). We observed in-situ photoferrotrophic activity through stimulation of phototrophic carbon uptake in the presence of Fe(II), and determined light-dependent Fe(II)-oxidation by the natural chemocline microbiota. Moreover, a photoferrotrophic bacterium most closely related to Chlorobium ferrooxidans was enriched from the ferruginous water column. Our study for the first time demonstrates a direct link between anoxygenic photoferrotrophy and the anoxic precipitation of Fe(III)-oxides in a ferruginous water column, providing a plausible mechanism for the bacterial origin of BIFs before the advent of free oxygen. However, photoferrotrophs represent only a minor fraction of the anoxygenic phototrophic community with the majority apparently thriving by sulfur cycling, despite the very low sulfur content in the ferruginous chemocline of Lake La Cruz

Photoferrotrophy: Remains of an ancient photosynthesis in modern environments

© 2017 Camacho, Walter, Picazo and Zopfi. Photoferrotrophy, the process by which inorganic carbon is fixed into organic matter using light as an energy source and reduced iron [Fe(II)] as an electron donor, has been proposed as one of the oldest photoautotrophic metabolisms on Earth. Under the iron-rich (ferruginous) but sulfide poor conditions dominating the Archean ocean, this type of metabolism could have accounted for most of the primary production in the photic zone. Here we review the current knowledge of biogeochemical, microbial and phylogenetic aspects of photoferrotrophy, and evaluate the ecological significance of this process in ancient and modern environments. From the ferruginous conditions that prevailed during most of the Archean, the ancient ocean evolved toward euxinic (anoxic and sulfide rich) conditions and, finally, much after the advent of oxygenic photosynthesis, to a predominantly oxic environment. Under these new conditions photoferrotrophs lost importance as primary producers, and now photoferrotrophy remains as a vestige of a formerly relevant photosynthetic process. Apart from the geological record and other biogeochemical markers, modern environments resembling the redox conditions of these ancient oceans can offer insights into the past significance of photoferrotrophy and help to explain how this metabolism operated as an important source of organic carbon for the early biosphere. Iron-rich meromictic (permanently stratified) lakes can be considered as modern analogs of the ancient Archean ocean, as they present anoxic ferruginous water columns where light can still be available at the chemocline, thus offering suitable niches for photoferrotrophs. A few bacterial strains of purple bacteria as well as of green sulfur bacteria have been shown to possess photoferrotrophic capacities, and hence, could thrive in these modern Archean ocean analogs. Studies addressing the occurrence and the biogeochemical significance of photoferrotrophy in ferruginous environments have been conducted so far in lakes Matano, Pavin, La Cruz, and the Kabuno Bay of Lake Kivu. To date, only in the latter two lakes a biogeochemical role of photoferrotrophs has been confirmed. In this review we critically summarize the current knowledge on iron-driven photosynthesis, as a remains of ancient Earth biogeochemistry

Behavior of beryllium in the weathering environment and its delivery to the ocean

ISSN:0016-7037ISSN:1872-953

Biogeochemical sulfur cycling in the water column of a shallow stratified sea-water lake: Speciation and quadruple sulfur isotope composition

Concentrations of sulfate, sulfide and intermediate sulfur species as well as quadruple sulfur isotope compositions of sulfate, sulfide and zero-valent sulfur (ZVS) were analyzed in the water column of Lake Rogoznica (Croatia), a stratified marine euxinic lake. The chemocline in the lake, which was located at 8.5–9.5 m depth, supports a dense population of purple phototrophic sulfide oxidizing bacteria from the genus Chromatium. The highest ZVS (5.42 μmol L−1) and sulfite (1.13 μmol L−1) concentrations were detected at the chemocline. Thiocyanate concentrations up to 288 nmol L−1 were detected near the bottom of the lake. The thiocyanate profile suggests that it diffuses up from the sediment, where it may be produced by the reaction of cyanide with sulfide oxidation intermediates. Multiple sulfur isotope fractionations between sulfate and sulfide were consistent with a model finding that disproportionation is not a dominant process below the chemocline. Microbial sulfide oxidation was found to be the dominant process of the reoxidative part of the sulfur cycle. Despite the absence of a clear signal for sulfur disproportionation in multiple sulfur isotope values, δ34S fractionations between sulfate and sulfide were in the range of 43.8–45.2‰, is relatively large in comparison to most laboratory culturing studies. Our results suggest that such fractionation is achieved by microbial sulfate reduction alone, which is in agreement with metabolic models and recent laboratory studies

Closing in on the marine 238U/235U budget

Significant redox-driven variability in the ratio between the two long-lived U parent isotopes, 238U and 235U, has recently been discovered. Thus, the 238U/235U system provides a promising new tool to evaluate redox changes in the past using the geological record. For such reconstruction to be successful, however, the modern marine U isotope cycle needs to be quantified. Here we compile U isotope ratios for the global dissolved riverine U flux. A total of 30 river samples covering a range of catchment sizes, latitudes, climates and continents were measured. Although variability is observed, the mean 238U/235U in the dissolved riverine U flux entering the ocean is close to the average for the continental crust, suggesting only minor 238U/235U fractionation during U weathering and transport. This riverine data is complemented by U isotope data in reducing sediments, the main oceanic U sink. Reducing sediments from an oxygen minimum zone off the coast of Washington State USA, show authigenic U accumulation with elevated 238U/235U compared to seawater, consistent with observations in other reducing marine sediments. However, these data also highlight that isotope partitioning between sediment and pore-water can cause variability in the 238U/235U of the accumulated authigenic U. The new data from this study, placed in the context of the growing body of data on modern marine U isotope cycling, suggest that U could be at steady-state in the modern ocean