Linear and cyclic aliphatic carboxamides of the Murchison meteorite: hydrolyzable derivatives of amino acids and other carboxylic acids

Analyses of fractionated aqueous extracts of the Murchison meteorite by gas chromatography-mass spectrometry after silylation with N-methyl-N (tert-butyldimethylsilyl) trifluoroacetamide have revealed an extensive series of linear and cyclic aliphatic amides. These include monocarboxylic acid amides, dicarboxylic acid monoamides, hydroxy acid amides, lactams, carboxy lactams, lactims, N-acetyl amino acids, and substituted hydantoins. Numerous isomers and homologues through at least C8 were observed in all cases, except for the N-acetyl amino acids and hydantoins. Carboxy lactams, lactams, hydantoins, and N-acetyl amino acids are converted to amino acids by acid hydrolysis, thus, these compounds qualitatively account for the earlier observation of acid-labile amino acid precursors in meteoritic extracts. Laboratory studies of the spontaneous decomposition of N-carbamyl-alpha-amino acids and their dehydration products, the 5-substituted hydantoins, have led to the recognition of a series of aqueous phase reactions by which amino acids and cyanic acid/cyanate ion in the primitive parent body might have given rise to several of the observed classes of amides, as well as to monocarboxylic acids, dicarboxylic acids, and hydroxy acids. A previously undescribed reaction of 5-substituted hydantoins with cyanic acid/cyanate ion to give carboxamides of the 5-substituent groups was observed in the course of these studies. The presence of an extensive suite of amides in a CM chondrite appears to be consistent with the interstellar-parent body formation hypothesis for the organic compounds of these meteorites. The presence of carboxy lactams and lactams along with free amino acids suggests the possibility of further chemical evolution of meteorite amino acids by thermal polymerization. The cyclic amides, given their potential for hydrogen-bonded pair formation, might be considered candidate bases for a primitive sequence coding system.     

Selective Extraction Chemistry of Toxic Metal Sulfides from Sediments

Experimental evidence suggests that formation of metal sulfides in anoxic sediments limits the bioavailability of several toxic elements. Our ability to quantify the processes by which these metal sulfides form is dependent upon our ability to determine the speciation of solid phase metals in sediments. Our work indicates that an entire suite of Cu-Fe and Ni-Fe sulfide minerals can form upon the exposure of mackinawite to aqueous Cu and Ni. Furthermore, we have demonstrated that the solubility of pure metal sulfide minerals and their iron-metal derivatives in HCl directly correlates with the observed trends in the 'Degree of Trace Metal Pyritization' in natural sediments. Current extraction schemes cannot distinguish discrete trace metal sulfides from trace metals associated with pyrite.     

Organic carbon isotope ratios (δ13C) of Arctic Amerasian Continental shelf sediments

Organic matter origins are inferred from carbon isotope ratios ('¹³C) in recent continental shelf sediments and major rivers from 465 locations from the north Bering-Chukchi-East Siberian-Beaufort Sea, Arctic Amerasia. Generally, there is a cross-shelf increase in '¹³C, which is due to progressive increased contribution seaward of marine-derived organic carbon to surface sediments. This conclusion is supported by the correlations between sediment '¹³C, OC/N, and '¹⁵N. The sources of total organic carbon (TOC) to the Amerasian margin sediments are primarily from marine water-column phytoplankton and terrigenous C₃ plants constituted of tundra taiga and angiosperms. In contrast to more temperate regions, the source of TOC from terrigenous C₄ and CAM plants to the study area is probably insignificant because these plants do not exist in the northern high latitudes. The input of carbon to the northern Alaskan shelf sediments from nearshore kelp community (Laminaria solidungula) is generally insignificant as indicated by the absence of high sediment '¹³C values (-16.5 to -13.6‰) which are typical of the macrophytes. Our study suggests that the isotopic composition of sediment TOC has potential application in reconstructing temporal changes in delivery and accumulation of organic matter resulting from glacial-interglacial changes in sea level and environments. Furthermore, recycling and advection of the extensive deposits of terrestrially derived organic matter from land, or the wide Amerasian margin, could be a mechanism for elevating total CO₂ and pCO₂ in the Arctic Basin halocline.     

An extended Bayesian sediment fingerprinting mixing model for the full Bayes treatment of geochemical uncertainties

Recent advances in sediment fingerprinting research have seen Bayesian mixing models being increasingly employed as an effective method to coherently translate component uncertainties into source apportionment results. Here, we advance earlier work by presenting an extended Bayesian mixing model capable of providing a full Bayes treatment of geochemical uncertainties. The performance of the extended full Bayes model was assessed against the equivalent empirical Bayes model and traditional frequentist optimisation. The performance of models coded in different Bayesian software (JAGS and Stan) was also evaluated, alongside an assessment of model sensitivity to reduced source representativeness and nonconservative fingerprint behaviour. Results revealed comparable accuracy and precision for the full and empirical Bayes models across both synthetic and real sediment geochemistry datasets, demonstrating that the empirical treatment of source data here represents a close approximation of the full Bayes treatment. Contrasts in the performance of models coded in JAGS and Stan revealed that the choice of software employed can impact significantly upon source apportionment results. Bayesian models coded in Stan were the least sensitive to both reduced source representativeness and nonconservative fingerprint behaviour, indicating Stan as the preferred software for future Bayesian sediment fingerprinting studies. Whilst the frequentist optimisation generally yielded comparable accuracy to the Bayesian models, uncertainties around apportionment estimates were substantially greater and the frequentist model was less effective at dealing with nonconservative behaviour. Overall, the effective performance of the extended full Bayes mixing model coded in Stan represents a notable advancement in source apportionment modelling relative to previous approaches. Both the mixing model and the software comparisons presented here should provide useful guidelines for future sediment fingerprinting studies.     

Using wind run to predict sand drift

Conventional aeolian sand transport models relate mass transport rate to wind speed or shear velocity, usually expressed and empirically tested on a 1-s time scale. Projections of total sand delivery over long time scales based on these models are highly sensitive to any small bias arising from statistical fitting on empirical data. We analysed time series of wind speed and sand transport rate collected at 14 independent measurement stations on a beach during a prior field experiment. The results show that relating total sand drift to cumulative above-threshold wind run yields models which are more statistically robust when fitted on empirical data, generating smaller prediction errors when projected to longer time scales. Testing of different power exponents indicates that a linear relationship between sand drift and above-threshold wind run yields the best results. These findings inspire a speculative novel phenomenological model relating the mass flow of air in the boundary layer to the mass transport of sand over the surface. © 2020 John Wiley & Sons, Ltd.     

Filtering potential field data by modifying its amplitude and phase in the space domain

Potential field datasets are commonly broken down in the space domain into amplitude (total gradient, or analytic signal amplitude) and phase (tilt angle) components as part of the data processing and interpretation procedure. However, it is possible to reconstruct the data again in the space domain from the amplitude and phase, and if they have been modified then a filtered dataset will be produced. For example, modified derivatives and filters which are based on them (such as the tilt angle and the theta map) can be produced. In addition, the modification of the data amplitude prior to the reconstruction of the signal allows controllable automatic gain control filters to be designed. The procedures are demonstrated on aeromagnetic and gravity data from Southern Africa.     

Application of the equilibrium planform concept to natural beaches in Northern Ireland

The equilibrium planform concept (EPC) for bayed beaches has achieved wide currency in coastal morphodynamics. The north coast of Ireland comprises a series of discrete headland-embayment beaches within which waves and currents recycle a finite sediment volume. It is therefore an ideal setting in which to explore the applicability of the concept. Application of the approach to 9 embayment beaches on the north coast of Ireland provides some insights into the application of the concept. The planform of some beaches does correspond to that predicted while others do not. Those whose measured planform does not correspond to the predicted planform can be interpreted through, (a) difficulty in identifying the wave diffraction point, (b) disequilibrium on the beach (sediment scarcity or excess), (c) geological control of beach morphology. The subjectivity in selecting the diffraction point renders alternative explanations difficult and reduces the utility of the approach on natural shorelines, where significant irregularities render identification of such points difficult.     

Structure and sediment distribution in the western Bering Sea

Eleven seismic reflection profiles across Shirshov Ridge and the adjacent deep-water sedimentary basins (Komandorsky and Aleutian Basins) are presented to illustrate the sediment distribution in the western Bering Sea. A prominent seismic reflecting horizon, Reflector P (Middle—Late Miocene in age), is observed throughout both the Aleutian and Komandorsky Basins at an approximate subbottom depth of 1 km. This reflector is also present, in places, on the flanks and along the crest of Shirshov Ridge. The thickness of sediments beneath Reflector P is significantly different within the two abyssal basins. In the Aleutian Basin, the total subbottom depth to acoustic basement (basalt?) is about 4 km, while in the Komandorsky Basin the depth is about 2 km.Shirshov Ridge, a Cenozoic volcanic feature that separates the Aleutian and Komandorsky Basins, is an asymmetric bathymetric ridge characterized by thick sediments along its eastern flank and steep scarps on its western side. The southern portion of the ridge has more structural relief that includes several deep, sediment-filled basins along its summit.Velocity data from sonobuoy measurements indicate that acoustic basement in the Komandorsky Basin has an average compressional wave velocity of 5.90 km/sec. This value is considerably larger than the velocities measured for acoustic basement in the northwestern Aleutian Basin (about 5.00 km/sec) and in the central Aleutian Basin (5.40–5.57 km/sec). In the northwestern Aleutian Basin, the low-velocity acoustic basement may be volcaniclastic sediments or other indurated sediments that are overlying true basaltic basement. A refracting horizon with similar velocities (4.6–5.0 km/sec) as acoustic basement dips steeply beneath the Siberian continental margin, reaching a maximum subbottom depth of about 8 km. The thick welt of sediment at the base of the Siberian margin may be the result of sediment loading or tectonic depression prior to Late Cenozoic time.     

The importance of winter in annual ecosystem respiration in the High Arctic: effects of snow depth in two vegetation types

Winter respiration in snow-covered ecosystems strongly influences annual carbon cycling, underlining the importance of processes related to the timing and quantity of snow. Fences were used to increase snow depth from 30 to 150 cm, and impacts on respiration were investigated in heath and mesic meadow, two common vegetation types in Svalbard. We manually measured ecosystem respiration from July 2007 to July 2008 at a temporal resolution greater than previously achieved in the High Arctic (campaigns: summer, eight; autumn, six; winter, 17; spring, nine). Moisture contents of unfrozen soil and soil temperatures throughout the year were also recorded. The increased snow depth resulted in significantly higher winter soil temperatures and increased ecosystem respiration. A temperature–efflux model explained most of the variation of observed effluxes: meadows, 94 (controls) and 93% (fences); heaths, 84 and 77%, respectively. Snow fences increased the total non-growing season efflux from 70 to 92 (heaths) and from 68 to 125 g CO₂-C m⁻² (meadows). The non-growing season contributed to 56 (heaths) and 42% (meadows) of the total annual carbon respired. This proportion increased with deeper snow to 64% in both vegetation types. Summer respiration rates were unaffected by snow fences, but the total growing season respiration was lower behind fences because of the considerably delayed snowmelt. Meadows had higher summer respiration rates than heaths. In addition, non-steady state CO₂ effluxes were measured as bursts lasting several days during spring soil thawing, and when ice layers were broken to carry out winter efflux measurements.