Catalytic peptide hydrolysis by mineral surface: Implications for prebiotic chemistry

The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds.Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO₃ buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70 °C. Below 70 °C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70 °C in solution. At 70 °C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded ∼1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG → DKP + G mechanism, rather than via GGG → GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium in environments where amino acids were already highly concentrated, but that minerals may not significantly alter the expected solution-phase equilibria. Thus the abiotic synthesis of long peptides may have required activating agents, dry heating at higher temperatures, or some form of phase separation.     

Uniform half-plane elastodynamic problems by an approximate boundary element method

In this paper the applicability of an approximate Boundary Element Method to uniform half-plane elastodynamic problems is investigated. This method employs the concept of images to construct approximate fundamental solutions for the half-plane and does not require any half-plane surface discretization. The method is formulated in the frequency domain for the case of harmonic disturbances or the Laplace transform domain for the case of transient disturbances. In the latter case a numerical inversion of the transformed solution is necessary to obtain the time domain response. The proposed method can be used as an alternative to boundary element methods that either utilize the infinite plane fundamental solution and thus require a half-plane surface discretization, or employ the exact half-plane fundamental solution, which even though leads to no surface discretization, is of a very lengthy and complicated form. Two characteristics numerical examples are used to illustrate the proposed method and study its advantages and disadvantages.     

On a modal damping identification model for non-classically damped linear building structures subjected to earthquakes

A simple modal damping identification model developed by the present authors for classically damped linear building frames is extended here to the non-classically damped case. The modal damping values are obtained with the aid of the frequency domain modulus of the roof-to-basement transfer function and the resonant frequencies of the structure (peaks of the transfer function) as well as the modal participation factors and mode shapes of the undamped structure. The assumption is made that the modulus of the transfer function of the non-classically damped structure matches the one of the classically damped structure in a discrete manner, i.e., at the resonant frequencies of that function modulus. This proposed approximate identification method is applied to a number of plane building frames with and without pronounced non-classical damping under different with respect to their frequency content earthquakes and its limitations and range of applicability are assessed with respect to the accuracy of both the identified damping ratios and that of the seismic structural response obtained by classical mode superposition and use of those identified modal damping ratios.     

Late Miocene to Quaternary slip history across the Qiulitag anticline in the southern Tianshan piedmont

In this study, we reconstruct the Miocene to Quaternary shortening history across the Qiulitag anticline, a complex fault‐bend fold located in southern Tianshan. We studied the Yaha and Kuche sections, where we combined surface structural measurements and seismic imaging to model the stratigraphic horizons. The history of folding was reconstructed based on magnetostratigraphic analyses and eight cosmogenic burial ages in Kuche. Pleistocene deformation rates were also quantified in Yaha based on a deformed fluvial terrace that we dated to ~67 ka using a cosmogenic depth profile. Our results suggest that the fold grew at a mean slip rate of 0.9–1.3 mm/a in both sections but accelerated to ~2.5 mm/a during the Pleistocene in Kuche. These results support a migration of the deformation towards the basin during the Pleistocene and suggest that most of the present deformation in the Tianshan is accommodated across the external structures of the range.     

Storylines: an alternative approach to representing uncertainty in physical aspects of climate change

Investigating the relationships between climate extremes and crop yield can help us understand how unfavourable climatic conditions affect crop production. In this study, two statistical models, multiple linear regression and random forest, were used to identify rainfall extremes indices affecting wheat yield in three different regions of the New South Wales wheat belt. The results show that the random forest model explained 41–67% of the year-to-year yield variation, whereas the multiple linear regression model explained 34–58%. In the two models, 3-month timescale standardized precipitation index of Jun.–Aug. (SPI_JJA), Sep.–Nov. (SPI_SON), and consecutive dry days (CDDs) were identified as the three most important indices which can explain yield variability for most of the wheat belt. Our results indicated that the inter-annual variability of rainfall in winter and spring was largely responsible for wheat yield variation, and pre-growing season rainfall played a secondary role. Frequent shortages of rainfall posed a greater threat to crop growth than excessive rainfall in eastern Australia. We concluded that the comparison between multiple linear regression and machine learning algorithm proposed in the present study would be useful to provide robust prediction of yields and new insights of the effects of various rainfall extremes, when suitable climate and yield datasets are available.     

An archetype hydrogen atmosphere problem

Populations for the first three bound states and the continuum of hydrogen are determined for an isothermal, hydrostatic atmosphere at 20 000 K. The atmosphere is treated as being optically thin in the Balmer and Paschen continua and illuminated by continuum radiation at these wavelengths with prescribed radiation temperatures. The atmosphere is optically thick in the 2-1, 3-1, 3-2 and c-1 transitions. Three stages of approximation are treated:

1. radiative detailed balance in the 2-1, 3-1 and 3-2 transitions,
2. radiative detailed balance in the 3-1 and 3-2 transitions, and
3. all transitions out of detailed balance.

The solution of this problem is non-trivial, and presents sufficient difficulty to have caused failure of at least one rather standard technique. The problem is thus a good archetype against which new methods, or new implementations of old methods may be tested.     

Spatio-temporal changes in totally and enzymatically hydrolyzable amino acids of superficial sediments from three contrasted areas

Spatio-temporal changes in totally and enzymatically hydrolyzable amino acids (THAA and EHHA) and EHAA/THAA ratios of superficial sediments were assessed during 1997-1999 in three areas (i.e., the Gulf of Lions, the Bay of Biscay, and Central Chile) differing in their primary productivity. In all three areas, and even off Central Chile where a strong El Niño event took place during 1997-1998, spatial changes were always much greater than temporal ones. The factors affecting the spatial distributions of amino acid concentrations differed among areas. In the Gulf of Lions, sediment granulometry was apparently the most important driving force of THAA, EHAA, and EHAA/THAA, and there was no marked difference between stations located on the open slope and those in submarine canyons. Conversely, in the Bay of Biscay, there were clear differences between the stations located off Cap-Breton, on the open slope, and those in the Cap-Ferret canyon; the latter two featuring lower EHAA and THAA but higher EHAA/THAA. This pattern is likely to result from the predominance of different sources of organic matter and especially from the importance of continental inputs to the Cap-Breton canyon. Off Central Chile, amino acid concentrations and ratios were both maximal around 100 m depth, probably reflecting the interaction between the primary productivity gradient and the presence of an oxygen minimum zone (OMZ) reducing the degradation of sedimentary organics. When comparing the average values collected in the three areas studied, THAA and EHAA were highest in Central Chile, intermediate in the Bay of Biscay and lowest in the Gulf of Lions. EHAA/THAA ratios were also highest in Central Chile but were lowest in the Bay of Biscay. Differences between the Gulf of Lions and the Bay of Biscay could have been affected by sampling design. In Central Chile, the use of labile organic carbon to total organic carbon (C-LOM/TOC) and EHAA/THAA as indices of organic matter lability led to very similar results. This was not the case in the Bay of Biscay. It is therefore argued that the use of C-LOM/TOC should be restricted to highly productive areas.     

Evidence for enhanced bioavailability of trace elements in the marine ecosystem of Deception Island, a volcano in Antarctica

This study assessed whether trace elements present at Deception Island, an active submarine volcano in the Antarctic Peninsula, show enhanced biological availability to the local marine community. Using a weak acid extraction method to dissolve organic material and leach associated but not constitutive trace elements of sediments, fifteen elements were measured from seafloor sediment, seawater particulates, and tissues of benthic (bivalves, brittlestars, sea urchins) and pelagic (demersal and pelagic fishes, krill) organisms collected in the flooded caldera. The highest element concentrations were associated with seafloor sediment, the lowest with seawater particulates and organism tissues. In the case of Ag and Se, concentrations were highest in organism tissue, indicating contamination through the food chain and biomagnification of those elements. The elements Al, Fe, Mn, Sr, Ti, and to a lesser extent Zn, were the most concentrated of the trace elements for all sample types. This indicates that the whole ecosystem of Deception Island is contaminated with trace elements from local geothermal activity, which is also reflected in the pattern of element contamination in organisms. Accordingly, element concentrations were higher in organisms collected at Deception Island compared to those from the neighboring non-active volcanic King George Island, suggesting that volcanic activity enhances bioavailability of trace elements to marine organisms. Trace element concentrations were highest in digestive tissue of organisms, suggesting that elements at Deception Island are incorporated into the marine food web mainly through a dietary route.