Radiocarbon ages and major n-alkane homologues of peat cores LVPS4 and LVPS5B, Russian Arctic

Coupled analyses of n-alkane biomarkers and plant macrofossils from a peat plateau deposit in the northeast European Russian Arctic were carried out to assess the effects of past hydrology on the molecular contributions of plants to the peat. The n-alkane biomarkers accumulated over 9.6 kyr of local paleohydrological changes in this complex peat profile in which a succession of vegetation changes occurred during a transition from a wet fen to a relatively dry peat plateau bog. This study shows that the contribution of the n-C31 alkane from rootlets to peat layers rich in fine and dark roots is important. The results further indicate that the n-alkane Paq and n-C23/n-C29 biomarker proxies that have been useful to reconstruct past water table levels in many peat deposits can be misleading when the contributions of Betula and Sphagnum fuscum to the peat are large. Under these conditions, the C23/(C27 + C31) n-alkane ratio seems to correct for the presence of Betula and S. fuscum and provides a better description for the relative amounts of moisture. The average chain length (ACL) n-alkane proxy also appears to be a good paleohydrology proxy in having larger values during dry and cold conditions in this Arctic bog setting.

Chemistry of secondary minerals from the deep sheeted dike complex of ODP Holes 137-504B and 140-504B

Dolerites sampled from the lower sheeted dikes from Hole 504B during Ocean Drilling Program Legs 137 and 140, between 1562.4 and 2000.4 mbsf, were examined to document the mineralogy, petrography, and mineral parageneses associated with secondary alteration, to constrain the thermal history and composition of hydrothermal fluids. The main methods used were mineral chemical analyses by electron microprobe, X-ray diffraction, and cathodoluminescence microscopy. Temperatures of alteration were estimated on the basis of single and/or coexisting mineral chemistry. Permeability is important in controlling the type and extent of alteration in the studied dike section. At the meter-scale, intervals of weakly altered dolerites containing fresh olivine are interpreted as having experienced restricted exposure to hydrothermal fluids. At the centimeter- or millimeter-scale, alteration patches and extensively altered halos adjacent to veins reflect the permeability related to intergranular primary porosity and cracks. Most of the sheeted dike alteration in this case resulted from non-focused, pervasive fluid-rock interaction. This study confirms and extends the previous model for hydrothermal alteration at Hole 504B: hydrothermal alteration at the ridge axis followed by seawater recharge and off-axis alteration. The major new discoveries, all related to higher temperatures of alteration, are: (1) the presence of hydrothermal plagioclase (An80-95), (2) the presence of deuteric and/or hydrothermal diopside, and (3) the general increasing proportion of amphiboles, and particularly magnesio-hornblende with depth. We propose that the dolerites at Hole 504B were altered in five stages. Stage 1 occurred at high temperatures (less than 500° to 700°C) and involved late-magmatic formation of Na- and Ti-rich diopside, the hydrothermal formation of Na, Ti-poor diopside and the hydrothermal formation of an assemblage of An-rich plagioclase + hornblende. Stage 2 occurred at lower temperatures (250°-320°C) and is characterized by the appearance of actinolite, chlorite, chlorite-smectite, and/or talc (in low permeability zones) and albite. During Stage 3, quartz and epidote precipitated from evolved hydrothermal fluids at temperatures between 310° and 320°C. Anhydrite appeared during Stage 4 and likely precipitated directly from heated seawater. Stage 5 occurred off-axis at low temperatures (250°C) with laumontite and prehnite from evolved fluids.

Emotions and the Engineering of Adaptiveness in Complex Systems

A major challenge in the engineering of complex and critical systems is the management of change, both in the system and in its operational environment. Due to the growing of complexity in systems, new approaches on autonomy must be able to detect critical changes and avoid their progress towards undesirable states. We are searching for methods to build systems that can tune the adaptability protocols. New mechanisms that use system-wellness requirements to reduce the influence of the outer domain and transfer the control of uncertainly to the inner one. Under the view of cognitive systems, biological emotions suggests a strategy to configure value-based systems to use semantic self-representations of the state. A method inspired by emotion theories to causally connect to the inner domain of the system and its objectives of wellness, focusing on dynamically adapting the system to avoid the progress of critical states. This method shall endow the system with a transversal mechanism to monitor its inner processes, detecting critical states and managing its adaptivity in order to maintain the wellness goals. The paper describes the current vision produced by this work-in-progress.

Emotions and the Engineering of Adaptiveness in Complex Systems

A major challenge in the engineering of complex and critical systems is the management of change, both in the system and in its operational environment. Due to the growing of complexity in systems, new approaches on autonomy must be able to detect critical changes and avoid their progress towards undesirable states. We are searching for methods to build systems that can tune the adaptability protocols. New mechanisms that use system-wellness requirements to reduce the influence of the outer domain and transfer the control of uncertainly to the inner one. Under the view of cognitive systems, biological emotions suggests a strategy to configure value-based systems to use semantic self-representations of the state. A method inspired by emotion theories to causally connect to the inner domain of the system and its objectives of wellness, focusing on dynamically adapting the system to avoid the progress of critical states. This method shall endow the system with a transversal mechanism to monitor its inner processes, detecting critical states and managing its adaptivity in order to maintain the wellness goals. The paper describes the current vision produced by this work-in-progress.

NMR determination of the major solution conformation of a peptoid pentamer with chiral side chains

Polymers of N-substituted glycines (“peptoids”) containing chiral centers at the α position of their side chains can form stable structures in solution. We studied a prototypical peptoid, consisting of five para-substituted (S)-N-(1-phenylethyl)glycine residues, by NMR spectroscopy. Multiple configurational isomers were observed, but because of extensive signal overlap, only the major isomer containing all cis-amide bonds was examined in detail. The NMR data for this molecule, in conjunction with previous CD spectroscopic results, indicate that the major species in methanol is a right-handed helix with cis-amide bonds. The periodicity of the helix is three residues per turn, with a pitch of ≈6 Å. This conformation is similar to that anticipated by computational studies of a chiral peptoid octamer. The helical repeat orients the amide bond chromophores in a manner consistent with the intensity of the CD signal exhibited by this molecule. Many other chiral polypeptoids have similar CD spectra, suggesting that a whole family of peptoids containing chiral side chains is capable of adopting this secondary structure motif. Taken together, our experimental and theoretical studies of the structural properties of chiral peptoids lay the groundwork for the rational design of more complex polypeptoid molecules, with a variety of applications, ranging from nanostructures to nonviral gene delivery systems.