Global fjords as transitory reservoirs of labile organic carbon modulated by organo-mineral interactions.

The global carbon cycle is strongly modulated by organic carbon (OC) sequestration and decomposition. Whereas OC sequestration is relatively well constrained, there are few quantitative estimates of its susceptibility to decomposition. Fjords are hot spots of sedimentation and OC sequestration in marine sediments. Here, we adopt fjords as model systems to investigate the reactivity of sedimentary OC by assessing the distribution of the activation energy required to break OC bonds. Our results reveal that OC in fjord sediments is more thermally labile than that in global sediments, which is governed by its unique provenance and organo-mineral interactions. We estimate that 61 ± 16% of the sedimentary OC in fjords is degradable. Once this OC is remobilized and remineralized during glacial maxima, the resulting metabolic CO2 could counterbalance up to 50 ppm of the atmospheric CO2 decrease during glacial times, making fjords critical actors in dampening glacial-interglacial climate fluctuations through negative carbon cycling loops.

Comparative soft-tissue preservation in Holocene-age capelin concretions.

Determining how soft tissues are preserved and persist through geologic time are continuing challenge because decay begins immediately after senescence while diagenetic transformations generally progress over days to millions of years. However, in recent years, carbonate concretions containing partially-to-fully decayed macroorganisms have proven to be remarkable windows into the diagenetic continuum revealing insights into the fossilization process. This is because most concretions are the result of biologically induced mineral precipitation caused by the localized decay of organic matter, which oftentimes preserves a greater biological signal relative to their host sediment. Here we present a comparative lipid biomarker study investigating processes associated with soft-tissue preservation within Holocene-age carbonate concretions that have encapsulated modern capelin (Mallotus villosus). We focus on samples collected from two depositional settings that have produced highly contrasting preservation end-members: (1) Kangerlussuaq, Greenland: a marine environment, which, due to isostatic rebound, has exposed strata containing concretions exhibiting exceptional soft-tissue preservation (6-7 kya), and (2) Greens Creek, Ottawa, Canada: a paleo brackish-to-freshwater marine excursion containing concretions exhibiting skeletal remains (~11 kya). Lipid biomarker analysis reveals endogenous capelin tissues and productive waters at Kangerlussuaq that are in sharp contrast to Greens Creek concretions, which lack appreciable capelin and environmental signals. Comparable distributions of bacterial fatty acids and statistical analyses suggest soft-tissue preservation within concretions is agnostic to specific heterotrophic decay communities. We, therefore, interpret preservation within carbonate concretions may represent a race between microbially induced authigenic precipitation and decay. Namely, factors resulting in exceptional preservation within concretions likely include: (1) organic matter input, (2) rate of decay, (3) carbonate saturation, (4) porewater velocity, and (5) rate of authigenic (carbonate) precipitation resulting in arrested decay/bacterial respiration due to cementing pore spaces limiting the diffusion of electron acceptors into the decay foci.

Carotenoid biomarkers in Namibian shelf sediments: Anoxygenic photosynthesis during sulfide eruptions in the Benguela Upwelling System.

Aromatic carotenoid-derived hydrocarbon biomarkers are ubiquitous in ancient sediments and oils and are typically attributed to anoxygenic phototrophic green sulfur bacteria (GSB) and purple sulfur bacteria (PSB). These biomarkers serve as proxies for the environmental growth requirements of PSB and GSB, namely euxinic waters extending into the photic zone. Until now, prevailing models for environments supporting anoxygenic phototrophs include microbial mats, restricted basins and fjords with deep chemoclines, and meromictic lakes with shallow chemoclines. However, carotenoids have been reported in ancient open marine settings for which there currently are no known modern analogs that host GSB and PSB. The Benguela Upwelling System offshore Namibia, known for exceptionally high primary productivity, is prone to recurrent toxic gas eruptions whereupon hydrogen sulfide emanates from sediments into the overlying water column. These events, visible in satellite imagery as water masses clouded with elemental sulfur, suggest that the Benguela Upwelling System may be capable of supporting GSB and PSB. Here, we compare distributions of biomarkers in the free and sulfur-bound organic matter of Namibian shelf sediments. Numerous compounds-including acyclic isoprenoids, steranes, triterpanes, and carotenoids-were released from the polar lipid fractions upon Raney nickel desulfurization. The prevalence of isorenieratane and ß-isorenieratane in sampling stations along the shelf verified anoxygenic photosynthesis by low-light-adapted, brown-colored GSB in this open marine setting. Renierapurpurane was also present in the sulfur-bound carotenoids and was typically accompanied by lower abundances of renieratane and ß-renierapurpurane, thereby identifying cyanobacteria as an additional aromatic carotenoid source.

Molecular and isotopic evidence reveals the end-Triassic carbon isotope excursion is not from massive exogenous light carbon.

The negative organic carbon isotope excursion (CIE) associated with the end-Triassic mass extinction (ETE) is conventionally interpreted as the result of a massive flux of isotopically light carbon from exogenous sources into the atmosphere (e.g., thermogenic methane and/or methane clathrate dissociation linked to the Central Atlantic Magmatic Province [CAMP]). Instead, we demonstrate that at its type locality in the Bristol Channel Basin (UK), the CIE was caused by a marine to nonmarine transition resulting from an abrupt relative sea level drop. Our biomarker and compound-specific carbon isotopic data show that the emergence of microbial mats, influenced by an influx of fresh to brackish water, provided isotopically light carbon to both organic and inorganic carbon pools in centimeter-scale water depths, leading to the negative CIE. Thus, the iconic CIE and the disappearance of marine biota at the type locality are the result of local environmental change and do not mark either the global extinction event or input of exogenous light carbon into the atmosphere. Instead, the main extinction phase occurs slightly later in marine strata, where it is coeval with terrestrial extinctions and ocean acidification driven by CAMP-induced increases in Pco2; these effects should not be conflated with the CIE. An abrupt sea-level fall observed in the Central European basins reflects the tectonic consequences of the initial CAMP emplacement, with broad implications for all extinction events related to large igneous provinces.

Biomarker stratigraphy in the Athel Trough of the South Oman Salt Basin at the Ediacaran-Cambrian Boundary.

The South Oman Salt Basin (SOSB) has been studied extensively for knowledge concerning the habitat of the enigmatic Ediacaran-Cambrian oils that are produced from that region. Geological, geochemical, geophysical, and geochronological investigations have all contributed to improved understanding of the range of late Neoproterozoic depositional environments recorded there. Of particular interest has been the deep Athel depocenter within the SOSB that features a silica-rich interval known as the Al Shomou Member or Athel Silicilyte and the co-eval A4 carbonate-evaporite sequence that straddles the Ediacaran-Cambrian boundary. The deep basin has been suggested to be anoxic and euxinic based on studies of sulfur isotopes, trace metal distributions and other proxies. Organic geochemistry has provided some clues concerning aspects of the depositional environments and microbial communities prevailing during this interval. However, ambiguities remain including a paucity of convincing molecular evidence for euxinia in the photic zone of the basin. Here, we present a comprehensive study of biomarker hydrocarbons, including steroids, triterpenoids, and carotenoids. Among the compounds detected is a distinctive array of aromatic carotenoids. Relatively low abundances of monoaromatic carotenoids, such as chlorobactane, okenane, and ß-isorenieratane, suggest the possibility of transient photic zone euxinia with a shallow chemocline or, perhaps, exogenous inputs from microbial mats. However, it is the dominance of renieratane and renierapurpurane over isorenieratane in diaromatic carotenoids and their association with abundant C38 and C39 carotenoids that identifies cyanobacteria as major contributors to the inventory of carotenoids. Our results, based on multiple lines of molecular evidence and statistical analysis, also suggest that the Athel Silicilyte was biogeochemically distinct from the other units of the Ara Group. Overall, our study has important implications for understanding other late Neoproterozoic depositional environments.

Niche expansion for phototrophic sulfur bacteria at the Proterozoic-Phanerozoic transition.

Fossilized carotenoid hydrocarbons provide a window into the physiology and biochemistry of ancient microbial phototrophic communities for which only a sparse and incomplete fossil record exists. However, accurate interpretation of carotenoid-derived biomarkers requires detailed knowledge of the carotenoid inventories of contemporary phototrophs and their physiologies. Here we report two distinct patterns of fossilized C40 diaromatic carotenoids. Phanerozoic marine settings show distributions of diaromatic hydrocarbons dominated by isorenieratane, a biomarker derived from low-light-adapted phototrophic green sulfur bacteria. In contrast, isorenieratane is only a minor constituent within Neoproterozoic marine sediments and Phanerozoic lacustrine paleoenvironments, for which the major compounds detected are renierapurpurane and renieratane, together with some novel C39 and C38 carotenoid degradation products. This latter pattern can be traced to cyanobacteria as shown by analyses of cultured taxa and laboratory simulations of sedimentary diagenesis. The cyanobacterial carotenoid synechoxanthin, and its immediate biosynthetic precursors, contain thermally labile, aromatic carboxylic-acid functional groups, which upon hydrogenation and mild heating yield mixtures of products that closely resemble those found in the Proterozoic fossil record. The Neoproterozoic-Phanerozoic transition in fossil carotenoid patterns likely reflects a step change in the surface sulfur inventory that afforded opportunities for the expansion of phototropic sulfur bacteria in marine ecosystems. Furthermore, this expansion might have also coincided with a major change in physiology. One possibility is that the green sulfur bacteria developed the capacity to oxidize sulfide fully to sulfate, an innovation which would have significantly increased their capacity for photosynthetic carbon fixation.

Spatiotemporal variability of hydrocarbons in surface sediments from an intensively human-impacted Xiaoqing River-Laizhou Bay system in the eastern China: Occurrence, compositional profile and source apportionment.

Hydrocarbons in coastal sediments record organic matter sources, and thus are widely used to elucidate both natural and anthropogenic inputs and for the estimation of pollution levels. Surface sediments were taken from Xiaoqing River and Laizhou Bay of eastern China in spring and summer of 2014, and were analyzed to determine the characteristics of aliphatic and aromatic hydrocarbons. Various hydrocarbons were identified, including n-alkanes, monomethylated alkanes (MMAs), isoprenoid alkanes, linear alkylbenzenes (LABs), hopanes, steranes and polycyclic aromatic hydrocarbons (PAHs). They were used to track both biogenic (terrestrial plant and microbial inputs) and anthropogenic inputs (petroleum and fossil fuel or biomass burning) in this ecosystem. The major part of hydrocarbons identified came from anthropogenic inputs including petroleum residues and synthetic detergents related hydrocarbons (16.2-90.3%), followed by higher plant (4.5-80.5%) and microbial inputs (0.8-57.5%). Interestingly, significant differences in hydrocarbon concentrations and distributions were observed between spring and summer. In particular, significant higher percentages of microbially derived hydrocarbons, but lower percentages of anthropogenic and vascular plant derived hydrocarbons were observed in summer than spring. Further principal component analyses suggested that the overall distribution of aliphatic hydrocarbons was mainly controlled by seasonality instead of spatiality. In contrast, the distribution of PAHs showed insignificant spatial and seasonal differences. Physical processes such as atmospheric transportation and further deposition, may be factors influencing the distribution of PAHs in the study area with widely biomass and fossil fuel burning. The decoupled distributions of aliphatic and aromatic hydrocarbons warrant further study for a comprehensive understanding of long term sedimentary hydrocarbon sources and input dynamics with increasing human activities. MAJOR FINDING: Seasonal difference in aliphatic hydrocarbon composition was observed in surface sediments of Laizhou Bay, which is mainly caused by stronger phytoplankton and microbial inputs in summer under the overall high pollution background.

Using fecal sterols to assess dynamics of sewage input in sediments along a human-impacted river-estuary system in eastern China.

Sedimentary fecal sterols and other sterol biomarkers, combined with bulk total organic carbon (TOC) and its stable carbon isotope were applied to characterize the sewage contamination across a ca. 280 km transect from the Xiaoqing River to the Laizhou Bay, a typical river-estuary system subjected to extensive anthropogenic stress due to rapid regional urbanization and industrialization in eastern China. Two sampling events were performed in both spring and summer seasons in the Laizhou Bay adjacent to the Xiaoqing River in order to assess the potential seasonal variation. Fecal sterols such as coprostanol and epicoprostanol, which are typical indicators of anthropogenic sewage input, displayed high concentrations of up to 63.2 µg g-1 dry weight (dw) and 13.1 µg g-1 dw, respectively. Results suggested that most of the stations along the Xiaoqing River were severely contaminated by fecal inputs with a decreasing trend from the river to the estuary that was mainly explained by the increasing distance from the diffuse sewage sources and the gradual dilution by sea water. Although there was no significant difference in fecal sterol concentrations between spring and summer in the Laizhou Bay, suggestive of no significant difference in sewage abundance, significantly higher average epicoprostanol/coprostanol and lower coprostanol/epicoprostanol ratios were observed in spring than summer, indicative of different sewage sources (e.g., human vs. non-human). Seasonal discharge and land-runoff, air temperature related to microbial activity differences and different extend of animal manure irrigation during agricultural planting could be additional reasons and need further investigation. Nevertheless, fecal sterol concentrations, distributions and diagnostic ratios should all be taken into consideration to better understand sewage inputs and source dynamics in river-estuary ecosystems.