Jets from Young Stellar Objects: Current Constraints and Challenges for the Future

I outline future directions of research that seem promising and necessary to identify the ejection process in YSO jets, including observational tests of ejection models, and challenging theoretical and observational issues.     

Biradical character of D-rich carriers in the insoluble organic matter of carbonaceous chondrites: A relic of the protoplanetary disk chemistry

The insoluble organic matter (IOM) of the Orgueil meteorite contains deuterium-rich radicals detectable by Electron Paramagnetic Resonance (EPR) techniques (Gourier et al., 2008). However the structure of these deuterium carriers remains poorly constrained. In this work, their electronic structure is deduced from the measurement of the spin states S by transient nutation in pulsed-EPR. It is shown that these deuterium-rich radicals are dominated by biradicaloids (species with S = 0 ground state and thermally accessible S = 1 state) and biradicals (species with S = 1 ground state) representing ∼61% and ∼31% of the radicals in the IOM of Orgueil, respectively, while single radicals (S = 1/2) contribute only to ∼8%. This is definitely different from mature terrestrial IOMs, which are known to contain almost exclusively S = 1/2 radicals. A structural model is proposed, whereby the occurrence of dominant biradicaloids and biradicals is the direct consequence of the structure of the IOM, made of a network of small aromatic moieties linked by branched and short aliphatic units. This implies that the formation of stable biradicaloids and biradicals by C-H breaking and their deuterium enrichment are produced after the formation of the IOM in the primitive solar system. These results reinforce the idea that the formation of the IOM and the deuterium-rich hotspots are the product of ion chemistry in the solar disk.     

Mono- and dicyclic unsaturated triterpenoid hydrocarbons in sediments from Lake Masoko (Tanzania) widely extend the botryococcene family

A mixture of C₃₃–C₃₇ botryococcenes and partially reduced derivatives was isolated from ca. 32,000 year old sediment from Lake Masoko, a freshwater crater lake in the Rungwe Range area (Tanzania). Botryococcenes and derivatives accounted for 246 μg/g dry sediment and for >92% of the hydrocarbon fraction; 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry allowed the structure of the dominant botryococcene (43% of hydrocarbon fraction) to be established, after purification using high performance liquid chromatography (HPLC). The compound is a novel tetraunsaturated dicyclic C₃₄ botryococcene and is named C₃₄ masokocene. Overall, the structures of six other novel botryococcenes and four partially reduced derivatives were tentatively assigned. The structures of the new biomarkers, three dicyclic C₃₄–C₃₆ botryococcenes (or masokocenes) and seven monocyclic C₃₄–C₃₇ analogues are discussed along with their biosynthetic relationship. The high abundance of such polyunsaturated compounds preserved in 32,000 year old sediment from the lake indicates an aquatic ecosystem dominated at the time by the green alga Botryococcus braunii, as well very good preservation of the organic matter.     

Oxidation of humic acids from an agricultural soil and a lignite deposit: Analysis of lipophilic and hydrophilic products

The composition of humic acids (HAs) isolated from an agricultural soil and a lignite deposit was examined via H₂O₂ and RuO₄ oxidation. The oxidation digests were separated into lipophilic and hydrophilic components. Information with regard to the source, degree of humification and preservation of easily degradable constituents of the HAs was obtained and results were compared with those obtained earlier for base hydrolysates of solvent-extracted fractions.H₂O₂ oxidation of both HAs afforded lipophilic fractions containing high molecular weight compounds. The composition of the base hydrolysates of the lipophilic fractions strongly differed with the origin of the HA. The lipophilic components of the soil HA derived mainly from the higher plant polyesters cutin and suberin. The lipophilic components of the lignite HA predominantly comprised long chain alkanoic acids and alkanols. The patterns for the hydrophilic components released upon H₂O₂ oxidation were found to be identical irrespective of the origin of the HA. The hydrophilic fractions comprised aliphatic (poly)carboxylic acids related to carbohydrate moieties and benzene polycarboxylic acids. The relative abundance of benzene polycarboxylic acids increased with the degree of humification.For both HAs, RuO₄ oxidation resulted in a lipophilic fraction containing low molecular weight products identical to those found in the base hydrolysate of the lipophilic fraction released upon H₂O₂ oxidation. The hydrophilic components released upon RuO₄ oxidation were independent of the HA origin and consisted mainly of monosaccharides and disubstituted aromatic compounds. In agreement with the greater aromaticity of lignite HA, the aromatic compound/carbohydrate ratio was higher for lignite HA than soil HA. The results show that the fused aromatic structures had a small size and that carbohydrates could escape degradation during the humification process.     

Intra-interstadial environmental changes in Last Glacial loess revealed by molluscan assemblages from the Upper Palaeolithic site of Amiens-Renancourt 1 (Somme,France)

The Amiens-Renancourt 1 site recently yielded one of the most important Upper Palaeolithic human occupations of northern France by the number of flint artefacts and especially by the presence of Venus figurines. All the material comes from a single archaeological layer located in a tundra gley bracketed by loess units. A multi-proxy study combining a detailed stratigraphy, luminescence and radiocarbon datings and high-resolution (5 cm per sample) grain size and molluscan analyses was therefore carried out to reconstruct and date the associated environmental changes and to determine the exact context of the human occupation. The chronological frame thus established supports the correlations of the archaeology-bearing tundra gley and of an underlying arctic brown soil with Greenland interstadials GI-4 and GI-3. Composition changes in the molluscan population enabled the identification of transitional and optimum phases and sub-phases within these two pedogenetic horizons. A conceptual correlation model linking molluscan phases with millennial-scale variations of Greenland ice-core and Sieben Hengste speleothem climate records is proposed. The Human occupation appears contemporaneous to the end of the stadial–interstadial transition of GI-3. Synchronous in Amiens-Renancourt 1 and Nussloch, subsequent micro-gleys may also result from a regional/global forcing. Such a level of detail is unprecedented in a loess sequence.     

Organic matter quality in reclaimed boreal forest soils following oil sands mining

Following surface mining of the Athabasca Oil Sands deposits in northeastern Alberta, Canada, land reclamation entails the reconstruction of soil-like profiles using salvaged soil materials such as peat and mining by-products. The overall objective of this research was to assess soil organic matter (SOM) quality in different reclamation practices as compared to undisturbed soils found in the region. Soil samples (0–10 cm) were taken from 45 plots selected to represent undisturbed reference ecosites and reclamation treatments. Soil OM pools were isolated using a combination of acid hydrolysis and physical separation techniques. Chemical composition of the low density fractions was characterized using ramped cross polarization (RAMP-CP) ¹³C nuclear magnetic resonance (NMR). Differences between disturbed and undisturbed sites reflected the influence of different botanical inputs (peat vs. forest litter) to SOM composition. Reconstructed soils were characterized by significantly lower alkyl over O-alkyl carbon (ALK/O-ALK) ratios (0.3) than undisturbed sites (0.5). For these reconstructed soils, a significantly higher proportion of soil carbon was present in the sand associated (Heavy sand) pool (49.2 vs. 37.3) and in the acid-unhydrolyzable residue (AUR) fraction (61.3 vs. 54.7). These SOM parameters were significantly related to time since reconstruction, with the AUR (p value = 0.012) and Heavy sand (p value = 0.05) fractions decreasing with time since reconstruction, while the ALK/O-ALK ratio increased (p value = 0.006). These findings suggest that the ALK/O-ALK, AUR, and Heavy sand parameters are suitable indicators for monitoring SOM quality in these reconstructed soils following oil sands mining.     

Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.     

A Parameterization of Dry Thermals and Shallow Cumuli for Mesoscale Numerical Weather Prediction

For numerical weather prediction models and models resolving deep convection, shallow convective ascents are subgrid processes that are not parameterized by classical local turbulent schemes. The mass flux formulation of convective mixing is now largely accepted as an efficient approach for parameterizing the contribution of larger plumes in convective dry and cloudy boundary layers. We propose a new formulation of the EDMF scheme (for Eddy Diffusivity\Mass Flux) based on a single updraft that improves the representation of dry thermals and shallow convective clouds and conserves a correct representation of stratocumulus in mesoscale models. The definition of entrainment and detrainment in the dry part of the updraft is original, and is specified as proportional to the ratio of buoyancy to vertical velocity. In the cloudy part of the updraft, the classical buoyancy sorting approach is chosen. The main closure of the scheme is based on the mass flux near the surface, which is proportional to the sub-cloud layer convective velocity scale w _*. The link with the prognostic grid-scale cloud content and cloud cover and the projection on the non- conservative variables is processed by the cloud scheme. The validation of this new formulation using large-eddy simulations focused on showing the robustness of the scheme to represent three different boundary layer regimes. For dry convective cases, this parameterization enables a correct representation of the countergradient zone where the mass flux part represents the top entrainment (IHOP case). It can also handle the diurnal cycle of boundary-layer cumulus clouds (EUROCS\ARM) and conserve a realistic evolution of stratocumulus (EUROCS\FIRE).     

Climate variability and trends in downscaled high-resolution simulations and projections over Metropolitan France

In order to fulfill the society demand for climate information at the spatial scale allowing impact studies, long-term high-resolution climate simulations are produced, over an area covering metropolitan France. One of the major goals of this article is to investigate whether such simulations appropriately simulate the spatial and temporal variability of the current climate, using two simulation chains. These start from the global IPSL-CM4 climate model, using two regional models (LMDz and MM5) at moderate resolution (15–20 km), followed with a statistical downscaling method in order to reach a target resolution of 8 km. The statistical downscaling technique includes a non-parametric method that corrects the distribution by using high-resolution analyses over France. First the uncorrected simulations are evaluated against a set of high-resolution analyses, with a focus on temperature and precipitation. Uncorrected downscaled temperatures suffer from a cold bias that is present in the global model as well. Precipitations biases have a season- and model-dependent behavior. Dynamical models overestimate rainfall but with different patterns and amplitude, but both have underestimations in the South-Eastern area (Cevennes mountains) in winter. A variance decomposition shows that uncorrected simulations fairly well capture observed variances from inter-annual to high-frequency intra-seasonal time scales. After correction, distributions match with analyses by construction, but it is shown that spatial coherence, persistence properties of warm, cold and dry episodes also match to a certain extent. Another aim of the article is to describe the changes for future climate obtained using these simulations under Scenario A1B. Results are presented on the changes between current and mid-term future (2021–2050) averages and variability over France. Interestingly, even though the same global climate model is used at the boundaries, regional climate change responses from the two models significantly differ.