Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

Komsomolskaya diamondiferous eclogites: evidence for oceanic crustal protoliths

The Komsomolskaya kimberlite is one of numerous (>1,000) kimberlite pipes that host eclogite xenoliths on the Siberian craton. Eclogite xenoliths from the adjacent Udachnaya kimberlite pipe have previously been geochemically well characterized; however, data from surrounding diamond-bearing kimberlite pipes from the center of the craton are relatively sparse. Here, we report major- and trace-element data, as well as oxygen isotope systematics, for mineral separates of diamondiferous eclogite xenoliths from the Komsomolskaya kimberlite, suggesting two distinct subgroups of a metamorphosed, subducted oceanic crustal protolith. Using almandine contents, this suite can be divided into two subgroups: group B1, with a high almandine component (>20 mol%) and group B2, with a low almandine component (<20 mol%). Reconstructed REE profiles for B1 eclogites overlap with typical oceanic basalts and lack distinct Eu anomalies. In addition, elevated oxygen isotope values, which are interpreted to reflect isotopic exchange with seawater at low temperatures (<350 °C), are consistent with an upper-oceanic crustal protolith. Reconstructed REE profiles for B2 eclogites are consistent with oceanic gabbros and display distinct Eu anomalies, suggesting a plagioclase-rich cumulate protolith. In contrast to B1, B2 eclogites do not display elevated oxygen isotope values, suggesting an origin deep within the crustal pile, where little-to-no interaction with hydrothermal fluids has occurred. Major-element systematics were reconstructed based on mineral modes; group B1 eclogites have higher MgO wt% and lower SiO₂ wt%, with respect to typical oceanic basalts, reflecting a partial melting event during slab subduction. Calculated residues from batch partial melt modeling of a range of Precambrian basalts overlap with group B1 trace-element chemistry. When taken together with the respective partial melt trajectories, these melting events are clearly linked to the formation of Tonalite–Trondhjemite–Granodiorite (TTG) complexes. As a result, we propose that many, if not all, diamondiferous eclogite xenoliths from Komsomolskaya represent mantle ‘restites’ that preserve chemical signatures of Precambrian oceanic crust.     

Cumulate gabbros from the Southwest Indian Ridge, 54°S-7° 16′ E: implications for magmatic processes at a slow spreading ridge

A diverse volcanic and plutonic rock suite was recovered from the center of the 80 km long ridge segment of the Southwest Indian Ridge (54°S, 7°16 E) between the Islas Orcadas and Shaka Fracture Zones. The cumulus nature of the gabbroic rocks in the suite is indicated by phase, modal and cryptic layering, igneous lamination, and low incompatible element abundances. We present a mass-balance model for calculating the proportions and compositions of cumulus phases and crystallized intercumulus liquid from bulk-rock major element compositions. The model is based on the ability to define a compositional array of basaltic liquids and on the assumption that cumulus minerals are initially in equilibrium with trapped liquid. Calculated proportions of trapped liquid range from 3%–15%; values that are characteristic of adcumulates to mesocumulates. Models of postcumulus crystallization indicate significant enrichments of incompatible elements and buffering of compatible elements in residual trapped liquids, thus explaining the high TiO₂ contents observed in magnesian clinopyroxenes. Cumulus phase assemblages and compositions suggest solidification in shallow level magma chambers, but disequilibrium plagioclase compositions suggest some crystallization at greater depth. Furthermore, basalt compositions projected onto the olivine-clinopyroxenequartz pseudoternary suggest magma generation over a range of pressures (from less than 10 to greater than 20 kb) as well as polybaric fractional crystallization. We suggest that the Southwest Indian Ridge is characterized by low magma supply with small batches of melt that either ascend directly to the surface having undergone limited polybaric crystallization or are trapped in shallow crustal magma chambers where they evolve and solidify to form cumulate gabbros. The adcumulus nature of the gabbros investigated here suggests slow cooling rates typical of large intrusions implying relatively large, but ephemeral magma chambers below segments of the Southwest Indian Ridge.     

Biological marker compounds as indicators of the depositions! history of the Maoming oil shale

The Eocene Maoming oil shale from Guangdong Province occurs as a laterally uniform stratigraphic section, typically 20–25 m thick, from which the aliphatic hydrocarbon constituents of six representative samples were investigated using GC and C-GC-MS. The sediments evaluated included the basal lignite, a vitrinite lens from the overlying claystone, and four intervals from the massive oil shale bed. As expected, the lignite and vitrinite differ markedly from the oil shales. The lignite is dominated by bacterial hopanoids and components of higher plant origin, including C₂₉ steroids and triterpenoids such as oleanenes. Visually, the oil shale samples show corroded and degraded phytoclasts, spores, wispy particles of fluorescent organic material attributable to dinoflagellates and, especially in the uppermost sample, colonial algal bodies. The distributions of biological markers in the oil shales show many features in common, notably a dominance of dinoflagellate-derived 4-methylsteroids, and a significant proportion of higher-plant derived n-alkanes with marked odd-over-even carbon number predominance. Overall, they exhibit several features that resemble characteristics of the Messel shale. The hydrocarbons of the lowest shale horizon suggest that there may have been a gradual transition between deposition of the original peat and the subsequent oil shales. The aliphatic hydrocarbons of the uppermost shale are dominated by a number of C₃₁ and C₃₃ botryococcane homologues and other unusual branched alkanes possibly derived from green algae. All of the samples are immature. Overall, molecular and microscopic examination of the stratigraphic succession of the Maoming oil shale suggests a shallow, lacustrine environment within which peats were deposited. This lake subsequently deepened to support abundant algal populations, especially dinoflagellates, culminating in a dominance of botryococcoid algae.     

A low temperature X-ray single-crystal diffraction and polarised infra-red study of epidote

The effects of low-temperature on the crystal structure of a natural epidote [Ca_1.925Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6)? and β = 115.396(8)° at room conditions, Sp. Gr. P2₁ /m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe³⁺ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000–2,500 cm⁻¹ are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)–O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe³⁺ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)–O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for “rigid body motions”. A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for “non-correlated motion”. The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U _eq (defined as one-third of the trace of the orthogonalised U _ij tensor) by ~40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U _eq of the octahedral and oxygen sites decrease similarly by ~35%, whereas those of the tetrahedral cations by ~22%.     

Bayesian modelling the retreat of the Irish Sea Ice Stream

We present an 8000‐year history spanning 650 km of ice margin retreat for the largest marine‐terminating ice stream draining the former British–Irish Ice Sheet. Bayesian modelling of the geochronological data shows the ISIS expanded 34.0–25.3 ka, accelerating into the Celtic Sea to reach maximum limits 25.3–24.5 ka before a collapse with rapid marginal retreat to the northern Irish Sea Basin (ISB). This retreat was rapid and driven by climatic warming, sea‐level rise, mega‐tidal amplitudes and reactivation of meridional circulation in the North Atlantic. The retreat, though rapid, is uneven, with the stepped retreat pattern possibly a function of the passage of the ice stream between normal and adverse ice bed gradients and changing ice stream geometry. Initially, wide calving margins and adverse slopes encouraged rapid retreat (～550 m a^?1) that slowed (～100 m a^?1) at the topographic constriction and bathymetric high between southern Ireland and Wales before rates increased (～200 m a^?1) across adverse bed slopes and wider and deeper basin configuration in the northern ISB. These data point to the importance of the ice bed slope and lateral extent in predicting the longer‐term (>1000 a) patterns and rates of ice‐marginal retreat during phases of rapid collapse, which has implications for the modelling of projected rapid retreat of present‐day ice streams. Copyright © 2013 John Wiley & Sons, Ltd.     

Interactive 3-D computation of fault surfaces using level sets

Deformable implicit surfaces, implemented with level set methods, have demonstrated a great potential in the computational sciences for applications such as modeling, simulation, and segmentation. They allow implicit handling of complex topologies deformed by operations where large changes can occur without destroying the level set representation. The use of level set techniques for the computation and segmentation of plane-like and high positive curvature features is nontrivial. We present a technique for representing and extracting fault surfaces from 3-D seismic attribute data such that 2-manifolds can be interactively computed and segmented. We present our approach as an interactive workflow that generates highly accurate fault surfaces.     

Shopping perceptions of the inner city elderly

This paper offers an exploratory investigation of two behavioural constructs of elderly shoppers: (i) spatial information fields and (ii) retail evaluation criteria. The constructs of the elderly are examined with reference to comparable responses of a baseline group of non-elderly consumers. The data are elicited from samples of elderly and non-elderly apartment dwellers in Winnipeg's central area. The results disclose that the spatial information fields of the elderly are relatively restricted, largely as a result of their lower levels of mobility. The problem of limited transport availability for the elderly is also expressed in terms of the higher levels of importance which they assign to accessibility factors in the decision on where to shop for groceries. In terms of other retail evaluation criteria, the elderly and non-elderly express different degrees of concern about various grocery outlet characteristics and commodity traits. It is concluded that the elderly represent a distinctive group of shoppers whose special characteristics may be relevant to the formulation of consumer spatial choice models.