Neodymium isotopes of central Mediterranean phosphatic hardgrounds reveal Miocene paleoceanography

Understanding the causes of the formation of hardgrounds provides insights on the oceanographic evolution of a basin. Phosphate-rich hardground formation interrupted carbonate ramp deposition in the Mediterranean during the Miocene. We analyzed the epsilon(Nd) record of three central Mediterranean hardgrounds to identify the origin of the phosphate-rich waters that formed them within the frame of Mediterranean Miocene paleoceanographic evolution. The Nd isotopes suggest that eastern Mediterranean deep waters were controlled by runoff, in contrast to Atlantic and Indian Ocean waters. This Nd isotope record attests to the weakening of Mediterranean circulation during the Miocene due to closure of the Indian Gateway. Limited exchange with Atlantic shallow seawater led to long residence times for deep waters in the basin. This record indicates the role of upwelling in formation of phosphate hardgrounds and shows the influence of global climate change and local paleoceanographic conditions

Reconstructing depositional rates and their effect on paleoenvironmental proxies : the case of the Lau Carbon Isotope Excursion in Gotland, Sweden

Variations in depositional rates affect the temporal depositional resolutions of proxies used for paleoenvironmental reconstructions; for example, condensation can make reconstructed environmental changes appear very abrupt. This is commonly addressed by transforming proxy data using age models, but this approach is limited to situations where numerical ages are available or can be reliably inferred by correlation. Here we propose a new solution, in which relative age models are constructed based on proxies for depositional rates. As a case study, we use the onset of the late Silurian Lau Carbon Isotope Excursion (LCIE) in Gotland, Sweden. The studied succession is a gradual record of shallowing upward in a tropical, neritic carbonate platform. As proxies for depositional rates we tested thorium concentration, carbonate content, and the concentration of pelagic palynomorphs. These three proxies were used to create relative age models using the previously published DAIME model. We applied these models to transform the delta C-13(carb) values as well as concentrations of selected redox-sensitive elements. The three relative age models yielded qualitatively similar results. In our case study, variations in depositional rates resulted in peaks of redox proxies appearing up to 76% higher when taken at face value, compared to when accounting for these rates. In the most extreme cases, our corrections resulted in a reversal in the stratigraphic trend of elemental concentrations. This approach can be applied and developed across depositional setting and types of paleoenvironmental proxies. It provides a flexible tool for developing quantitative models to improve our understanding of the stratigraphic record

The nature of Ordovician limestone-marl alternations in the Oslo-Asker District (Norway):witnesses of primary glacio-eustasy or diagenetic rhythms?

Ordovician limestone-marl alternations in the Oslo-Asker District have been interpreted as signaling glacio-eustatic lowstands, which would support a prolonged “Early Palaeozoic Icehouse”. However, these rhythmites could alternatively reflect differential diagenesis, without sedimentary trigger. Here, we test both hypotheses through one Darriwilian and three Katian sections. Our methodology consists of a bed-by-bed analysis of palynological (chitinozoan) and geochemical (XRF) data, to evaluate whether the limestone/marl couplets reflect an original cyclic signal. The results reveal similar palynomorph assemblages in limestones and marls. Exceptions, which could be interpreted as reflecting palaeoclimatological fluctuations, exist at the species level: Ancyrochitina bornholmensis seems to be more abundant in the marl samples from the lower Frognerkilen Formation on Nakkholmen Island. However, these rare cases where chitinozoans differ between limestone/marl facies are deemed insufficient for the identification of original cyclicity. The geochemical data show a near-perfect correlation between insoluble elements in the limestone and the marls, which indicates a similar composition of the potential precursor sediment, also in the Frognerkilen Formation. This is consistent with the palynological data. Although an original cyclic pattern could still be recorded by other, uninvestigated parameters, our palaeontological and geochemical data combined do not support the presence of such a signal

Metal-induced malformations in early Palaeozoic plankton are harbingers of mass extinction

Glacial episodes have been linked to Ordovician–Silurian extinction events, but cooling itself may not be solely responsible for these extinctions. Teratological (malformed) assemblages of fossil plankton that correlate precisely with the extinction events can help identify alternate drivers of extinction. Here we show that metal poisoning may have caused these aberrant morphologies during a late Silurian (Pridoli) event. Malformations coincide with a dramatic increase of metals (Fe, Mo, Pb, Mn and As) in the fossils and their host rocks. Metallic toxins are known to cause a teratological response in modern organisms, which is now routinely used as a proxy to assess oceanic metal contamination. Similarly, our study identifies metal-induced teratology as a deep-time, palaeobiological monitor of palaeo-ocean chemistry. The redox-sensitive character of enriched metals supports emerging ‘oceanic anoxic event’ models. Our data suggest that spreading anoxia and redox cycling of harmful metals was a contributing kill mechanism during these devastating Ordovician–Silurian palaeobiological events

Osmium and lithium isotope evidence for weathering feedbacks linked to orbitally paced organic carbon burial and Silurian glaciations

The Ordovician (∼487 to 443 Ma) ended with the formation of extensive Southern Hemisphere ice sheets, known as the Hirnantian glaciation, and the second largest mass extinction in Earth History. It was followed by the Silurian (∼443 to 419 Ma), one of the most climatically unstable periods of the Phanerozoic as evidenced by several large scale (> 5‰) carbon isotope (δ13C) perturbations associated with further extinction events. Despite several decades of research, the cause of these environmental instabilities remains enigmatic. Here, we provide osmium (187Os/188Os) and lithium (δ7Li) isotope measurements of marine sedimentary rocks that cover four Silurian δ13C excursions. Osmium and Li isotope records resemble those previously recorded for the Hirnantian glaciation suggesting a similar causal mechanism. When combined with a new dynamic carbon-osmium-lithium biogeochemical model we suggest that astronomical forcing of the marine organic carbon cycle, as opposed to a decline in volcanic arc degassing or the rise of early land plants, resulted in drawdown of atmospheric CO2, triggering continental scale glaciation, intense global cooling and eustatic sea-level lows recognised in the geological record. Lower atmospheric pCO2 and temperatures during the Hirnantian and Silurian glaciations suppressed CO2 removal by silicate weathering, driving 187Os/188Os and δ7Li variability, supporting the existence of climate-regulating feedbacks

Mineralization of Acephate, a Recalcitrant Organophosphate Insecticide Is Initiated by a Pseudomonad in Environmental Samples

An aerobic bacterium capable of breaking down the pesticide acephate (O,S-dimethyl acetyl phosphoramidothioic acid) was isolated from activated sludge collected from a pesticide manufacturing facility. A phylogenetic tree based on the 16 S rRNA gene sequence determined that the isolate lies within the Pseudomonads. The isolate was able to grow in the presence of acephate at concentrations up to 80 mM, with maximum growth at 40 mM. HPLC and LC-MS/MS analysis of spent medium from growth experiments and a resting cell assay detected the accumulation of methamidophos and acetate, suggesting initial hydrolysis of the amide linkage found between these two moieties. As expected, the rapid decline in acephate was coincident with the accumulation of methamidophos. Methamidophos concentrations were maintained over a period of days, without evidence of further metabolism or cell growth by the cultures. Considering this limitation, strains such as described in this work can promote the first step of acephate mineralization in soil microbial communities