Bart E. van Dongen

Differential mobilization of terrestrial carbon pools in Eurasian Arctic river basins

Mobilization of Arctic permafrost carbon is expected to increase with warming-induced thawing. However, this effect is challenging to assess due to the diverse processes controlling the release of various organic carbon (OC) pools from heterogeneous Arctic landscapes. Here, by radiocarbon dating various terrestrial OC components in fluvially and coastally integrated estuarine sediments, we present a unique framework for deconvoluting the contrasting mobilization mechanisms of surface vs. deep (permafrost) carbon pools across the climosequence of the Eurasian Arctic. Vascular plant-derived lignin phenol 14C contents reveal significant inputs of young carbon from surface sources whose delivery is dominantly controlled by river runoff. In contrast, plant wax lipids predominantly trace ancient (permafrost) OC that is preferentially mobilized from discontinuous permafrost regions, where hydrological conduits penetrate deeper into soils and thermokarst erosion occurs more frequently. Because river runoff has significantly increased across the Eurasian Arctic in recent decades, we estimate from an isotopic mixing model that, in tandem with an increased transfer of young surface carbon, the proportion of mobilized terrestrial OC accounted for by ancient carbon has increased by 3–6% between 1985 and 2004. These findings suggest that although partly masked by surface carbon export, climate change-induced mobilization of old permafrost carbon is well underway in the Arctic.

Nonconservative behavior of dissolved organic carbon across the Laptev and East Siberian seas

Climate change is expected to have a strong effect on the Eastern Siberian Arctic Shelf (ESAS) region, which includes 40% of the Arctic shelves and comprises the Laptev and East Siberian seas. The ...

Contrasting lipid biomarker composition of terrestrial organic matter exported from across the Eurasian Arctic by the five great Russian Arctic rivers

Contrasting lipid biomarker composition of terrestrial organic matter exported from across the Eurasian Arctic by the five great Russian Arctic rivers

Selective preservation of old organic carbon fluvially released from sub-Arctic soils

Amplified climate warming in the Arctic may cause thaw-remobilization of its large soil organic carbon (SOC) pool. Here we assess the remobilization and preservation of old SOC by the watershed-integrated radiocarbon signature of molecular SOC markers released from northernmost Scandinavia. The radiocarbon analyses revealed a remarkable fractionation for identical vascular plant markers (∼420‰ or ∼6000 14C years) upon settling from surface water to the underlying sediments. From this, we infer fluvial export of two SOC pools; a young surface peat component, and an old deep mineral soil component. The young pool exists as an easily degradable humic suspension, while the old pool is matrix protected from degradation and ballasted for preferential settling. The two soil types with highest OC in Arctic permafrost evidently exhibit different susceptibilities to degradation. Hence, a significant part of the thaw-released OC may simply be fluvially relocated to sediments instead of being emitted to the atmosphere.

Inventories and behavior of particulate organic carbon in the Laptev and East Siberian seas

Inventories and behavior of particulate organic carbon in the Laptev and East Siberian Seas

An interlaboratory study of TEX86 and BIT analysis of sediments, extracts, and standard mixtures

Two commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 (TetraEther indeX of 86 carbon atoms) paleothermometer for sea surface temperature reconstructions and the BIT (Branched Isoprenoid Tetraether) index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which 15 laboratories participated, showed relatively consistent TEX86 values (reproducibility +/- 3-4 degrees C when translated to temperature) but a large spread in BIT measurements (reproducibility +/- 0.41 on a scale of 0-1). Here we report results of a second round-robin study with 35 laboratories in which three sediments, one sediment extract, and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3 to 3.0 degrees C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the true (i.e., molar-based) BIT index. The latter is likely due to, among other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values.

Mineralized soft-tissue structure and chemistry in a mummified hadrosaur from the Hell Creek Formation, North Dakota (USA)

An extremely well-preserved dinosaur (Cf. Edmontosaurus sp.) found in the Hell Creek Formation (Upper Cretaceous, North Dakota) retains soft-tissue replacement structures and associated organic compounds. Mineral cements precipitated in the skin apparently follow original cell boundaries, partially preserving epidermis microstructure. Infrared and electron microprobe images of ossified tendon clearly show preserved mineral zonation, with silica and trapped carbon dioxide forming thin linings on Haversian canals within apatite. Furthermore, Fourier transform infrared spectroscopy (FTIR) of materials recovered from the skin and terminal ungual phalanx suggests the presence of compounds containing amide groups. Amino acid composition analyses of the mineralized skin envelope clearly differ from the surrounding matrix; however, intact proteins could not be obtained using protein mass spectrometry. The presence of endogenously derived organics from the skin was further demonstrated by pyrolysis gas chromatography mass spectrometry (Py-GCMS), indicating survival and presence of macromolecules that were in part aliphatic (see the electronic supplementary material).

An experimental study of the low-temperature sulfurization of carbohydrates

Sulfurization of carbohydrates has been suggested as an important mechanism for the preservation of organic matter. To study this process, different monosaccharides were sulfurized under laboratory conditions at relatively low temperature (50 °C). The products formed after cleavage of polysulfide linkages were analyzed using gas chromatography (GC) and gas chromatography/mass spectrometry after appropriate derivatization. Selected products were isolated by preparative GC and their structures were identified by nuclear magnetic resonance spectroscopy. During these experiments all monosaccharides were completely converted into organic sulfur compounds (OSCs) and monosaccharides with the carbonyl function replaced by sulfur formed a substantial part of the GC-amenable OSCs. The structures of other OSCs formed indicated that cleavage of C C bonds and racemization also took place during these experiments. The yield of recoverable OSCs after cleavage of polysulfide linkages was relatively low (<5% of the starting monosaccharide), indicating that most of the sulfurization products were still non GC-amenable and thus, for example, linked through monosulfide linkages. Flash pyrolysates of the sulfurized carbohydrate material contained in all cases relatively high amounts of short-chain alkylated (C0 C5) thiophenes, comparable to those obtained from S-rich kerogen. The structure of the monosaccharide used in the experiments had no effect on the alkylthiophene distribution. These results provide experimental evidence that sulfurization of monosaccharides at relatively low temperatures can result in the formation of OSCs, most likely starting with sulfurization of the carbonyl functionality. Preservation of carbohydrates through sulfurization may thus be an important pathway of preservation of organic matter in anoxic depositional environments.

Impact of Silver(I) on the Metabolism of Shewanella oneidensis

Anaerobic cultures of Shewanella oneidensis MR-1 reduced toxic Ag(I), forming nanoparticles of elemental Ag(0), as confirmed by X-ray diffraction analyses. The addition of 1 to 50 microM Ag(I) had a limited impact on growth, while 100 microM Ag(I) reduced both the doubling time and cell yields. At this higher Ag(I) concentration transmission electron microscopy showed the accumulation of elemental silver particles within the cell, while at lower concentrations the metal was exclusively reduced and precipitated outside the cell wall. Whole organism metabolite fingerprinting, using the method of Fourier transform infrared spectroscopy analysis of cells grown in a range of silver concentrations, confirmed that there were significant physiological changes at 100 microM silver. Principal component-discriminant function analysis scores and loading plots highlighted changes in certain functional groups, notably, lipids, amides I and II, and nucleic acids, as being discriminatory. Molecular analyses confirmed a dramatic drop in cellular yields of both the phospholipid fatty acids and their precursor molecules at high concentrations of silver, suggesting that the structural integrity of the cellular membrane was compromised at high silver concentrations, which was a result of intracellular accumulation of the toxic metal.

Morphological and geochemical evidence of eumelanin preservation in the feathers of the Early Cretaceous bird, Gansus yumenensis

Recent studies have shown evidence for the preservation of colour in fossilized soft tissues by imaging melanosomes, melanin pigment containing organelles. This study combines geochemical analyses with morphological observations to investigate the preservation of melanosomes and melanin within feathers of the Early Cretaceous bird, Gansus yumenensis. Scanning electron microscopy reveals structures concordant with those previously identified as eumelanosomes within visually dark areas of the feathers but not in lighter areas or sedimentary matrices. Fourier transform infrared analyses show different spectra for the feathers and their matrices; melanic functional groups appear in the feather including carboxylic acid and ketone groups that are not seen in the matrix. When mapped, the carboxylic acid group absorption faithfully replicates the visually dark areas of the feathers. Electron Paramagnetic Resonance spectroscopy of one specimen demonstrates the presence of organic signals but proved too insensitive to resolve melanin. Pyrolysis gas chromatography mass spectrometry shows a similar distribution of aliphatic material within both feathers that are different from those of their respective matrices. In combination, these techniques strongly suggest that not only do the feathers contain endogenous organic material, but that both geochemical and morphological evidence supports the preservation of original eumelanic pigment residue.