B. E. van Dongen

Activation of old carbon by erosion of coastal and subsea permafrost in Arctic Siberia.

The future trajectory of greenhouse gas concentrations depends on interactions between climate and the biogeosphere. Thawing of Arctic permafrost could release significant amounts of carbon into the atmosphere in this century. Ancient Ice Complex deposits outcropping along the ∼7,000-kilometre-long coastline of the East Siberian Arctic Shelf (ESAS), and associated shallow subsea permafrost, are two large pools of permafrost carbon, yet their vulnerabilities towards thawing and decomposition are largely unknown. Recent Arctic warming is stronger than has been predicted by several degrees, and is particularly pronounced over the coastal ESAS region. There is thus a pressing need to improve our understanding of the links between permafrost carbon and climate in this relatively inaccessible region. Here we show that extensive release of carbon from these Ice Complex deposits dominates (57 ± 2 per cent) the sedimentary carbon budget of the ESAS, the world’s largest continental shelf, overwhelming the marine and topsoil terrestrial components. Inverse modelling of the dual-carbon isotope composition of organic carbon accumulating in ESAS surface sediments, using Monte Carlo simulations to account for uncertainties, suggests that 44 ± 10 teragrams of old carbon is activated annually from Ice Complex permafrost, an order of magnitude more than has been suggested by previous studies. We estimate that about two-thirds (66 ± 16 per cent) of this old carbon escapes to the atmosphere as carbon dioxide, with the remainder being re-buried in shelf sediments. Thermal collapse and erosion of these carbon-rich Pleistocene coastline and seafloor deposits may accelerate with Arctic amplification of climate warming.

Arsenic release and attenuation in low organic carbon aquifer sediments from West Bengal

High arsenic concentrations in groundwater are causing a humanitarian disaster in Southeast Asia. It is generally accepted that microbial activities play a critical role in the mobilization of arsenic from the sediments, with metal-reducing bacteria stimulated by organic carbon implicated. However, the detailed mechanisms underpinning these processes remain poorly understood. Of particular importance is the nature of the organic carbon driving the reduction of sorbed As(V) to the more mobile As(III), and the interplay between iron and sulphide minerals that can potentially immobilize both oxidation states of arsenic. Using a multidisciplinary approach, we identified the critical factors leading to arsenic release from West Bengal sediments. The results show that a cascade of redox processes was supported in the absence of high loadings of labile organic matter. Arsenic release was associated with As(V) and Fe(III) reduction, while the removal of arsenic was concomitant with sulphate reduction. The microbial populations potentially catalysing arsenic and sulphate reduction were identified by targeting the genes arrA and dsrB, and the total bacterial and archaeal communities by 16S rRNA gene analysis. Results suggest that very low concentrations of organic matter are able to support microbial arsenic mobilization via metal reduction, and subsequent arsenic mitigation through sulphate reduction. It may therefore be possible to enhance sulphate reduction through subtle manipulations to the carbon loading in such aquifers, to minimize the concentrations of arsenic in groundwaters.

Infrared mapping resolves soft tissue preservation in 50 million year-old reptile skin

Non-destructive Fourier Transform InfraRed (FTIR) mapping of Eocene aged fossil reptile skin shows that biological control on the distribution of endogenous organic components within fossilized soft tissue can be resolved. Mapped organic functional units within this approximately 50 Myr old specimen from the Green River Formation (USA) include amide and sulphur compounds. These compounds are most probably derived from the original beta keratin present in the skin because fossil leaf- and other non-skin-derived organic matter from the same geological formation do not show intense amide or thiol absorption bands. Maps and spectra from the fossil are directly comparable to extant reptile skin. Furthermore, infrared results are corroborated by several additional quantitative methods including Synchrotron Rapid Scanning X-Ray Fluorescence (SRS-XRF) and Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS). All results combine to clearly show that the organic compound inventory of the fossil skin is different from the embedding sedimentary matrix and fossil plant material. A new taphonomic model involving ternary complexation between keratin-derived organic molecules, divalent trace metals and silicate surfaces is presented to explain the survival of the observed compounds. X-ray diffraction shows that suitable minerals for complex formation are present. Previously, this study would only have been possible with major destructive sampling. Non-destructive FTIR imaging methods are thus shown to be a valuable tool for understanding the taphonomy of high-fidelity preservation, and furthermore, may provide insight into the biochemistry of extinct organisms.

Leaf metallome preserved over 50 million years

Large-scale Synchrotron Rapid Scanning X-ray Fluorescence (SRS-XRF) elemental mapping and X-ray absorption spectroscopy are applied here to fossil leaf material from the 50 Mya Green River Formation (USA) in order to improve our understanding of the chemistry of fossilized plant remains. SRS-XRF of fossilized animals has previously shown that bioaccumulated trace metals and sulfur compounds may be preserved in their original distributions and these elements can also act as biomarkers for specific biosynthetic pathways. Similar spatially resolved chemical data for fossilized plants is sparsely represented in the literature despite the multitude of other chemical studies performed. Here, synchrotron data from multiple specimens consistently show that fossil leaves possess chemical inventories consisting of organometallic and organosulfur compounds that: (1) map discretely within the fossils, (2) resolve fine scale biological structures, and (3) are distinct from embedding sedimentary matrices. Additionally, the chemical distributions in fossil leaves are directly comparable to those of extant leaves. This evidence strongly suggests that a significant fraction of the chemical inventory of the examined fossil leaf material is derived from the living organisms and that original bioaccumulated elements have been preserved in situ for 50 million years. Chemical information of this kind has so far been unknown for fossilized plants and could for the first time allow the metallome of extinct flora to be studied.

The formation of ferromanganese nodules in the southwest Indian Ocean; an abiotic process

Abstract Ferromanganese nodules have been recognized widely as potentially important resources for strategic metals. However it remains unclear if the formation of these nodules is purely an abiotic process or if microorganisms are involved in their formation. To determine the microbial contributions, detailed organic geochemical analyses were performed on ferromanganese nodules collected from across the southwest Indian Ocean. These analyses reveal the presence of specific terrestrial, marine and petroleum derived biomarkers, consistent with formation in a marine setting with a substantial influx of terrestrially derived (higher plant detritus) and naturally occurring petroleum-related organic matter. In contrast, only trace amounts of general bacterial biomarkers, commonly present in these types of depositional environments, were present. This indicates that the formation of these ferromanganese nodules is predominantly an abiotic process although a minor contribution from microbial mediated processes to the growth of these nodules cannot be completely ruled out.