Solution structure of Mannobioses unravelled by means of Raman optical activity

Structural analysis of carbohydrates is a complicated endeavour, due to the complexity and diversity of the samples at hand. Herein, we apply a combined computational and experimental approach, employing molecular dynamics (MD) and density functional theory (DFT) calculations together with NMR and Raman optical activity (ROA) measurements, in the structural study of three mannobiose disaccharides, consisting of two mannoses with varying glycosidic linkages. The disaccharide structures make up the scaffold of high mannose glycans and are therefore important targets for structural analysis. Based on the MD population analysis and NMR, the major conformers of each mannobiose were identified and used as input for DFT analysis. By systematically varying the solvent models used to describe water interacting with the molecules and applying overlap integral analysis to the resulting calculational ROA spectra, we found that a full quantum mechanical/molecular mechanical approach is required for an optimal calculation of the ROA parameters. Subsequent normal mode analysis of the predicted vibrational modes was attempted in order to identify possible marker bands for glycosidic linkages. However, the normal mode vibrations of the mannobioses are completely delocalised, presumably due to conformational flexibility in these compounds, rendering the identification of isolated marker bands unfeasible

Recent seismic studies at the East Pacific Rise 8°20'–10°10'N and Endeavour Segment : insights into mid-ocean ridge hydrothermal and magmatic processes

Author Posting. © The Oceanography Society, 2012. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 25, no. 1 (2012): 100–112, doi:10.5670/oceanog.2012.08.As part of the suite of multidisciplinary investigations undertaken by the Ridge 2000 Program, new multichannel seismic studies of crustal structure were conducted at the East Pacific Rise (EPR) 8°20'–10°10'N and Endeavour Segment of the Juan de Fuca Ridge. These studies provide important insights into magmatic systems and hydrothermal flow in these regions, with broader implications for fast- and intermediate-spreading mid-ocean ridges. A mid-crust magma body is imaged beneath Endeavour Segment underlying all known vent fields, suggesting that prior notions of a tectonically driven hydrothermal system at this site can be ruled out. There is evidence at both sites that the axial magma body is segmented on a similar 5–20 km length scale, with implications for the geometry of high-temperature axial hydrothermal flow and for lava geochemistry. The new data provide the first seismic reflection images of magma sills in the crust away from the axial melt lens. These off-axis magma reservoirs are the likely source of more-evolved lavas typically sampled on the ridge flanks and may be associated with off-axis hydrothermal venting, which has recently been discovered within the EPR site. Clusters of seismic reflection events at the base of the crust are observed, and localized regions of thick Moho Transition Zone, with frozen or partially molten gabbro lenses embedded within mantle rocks, are inferred. Studies of the upper crust on the flanks of Endeavour Segment provide new insights into the low-temperature hydrothermal flow that continues long after crustal formation. Precipitation of alteration minerals due to fluid flow leads to changes in P-wave velocities within seismic Layer 2A (the uppermost layer of the oceanic crust) that vary markedly with extent of sediment blanketing the crust. In addition, intermediate-scale variations in the structure of Layers 2A and 2B with local topography are observed that may result from topographically driven fluid upflow and downflow on the ridge flanks.This research was supported by NSF OCE grants 0002488, 0002551, 0648303, 0648923, 0327872 and 0327885

A multi-sill magma plumbing system beneath the axis of the East Pacific Rise

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Nature Publishing Group for personal use, not for redistribution. The definitive version was published in Nature Geoscience 7 (2014): 825-829, doi:10.1038/ngeo2272.The mid-crust axial magma lens detected at fast and intermediate spreading mid-ocean ridges is believed to be the primary magma reservoir for formation of upper oceanic crust. However, the mechanism behind formation of the lower crust is a subject of ongoing debate. The sheeted sill model proposed from observations of ophiloites requires the presence of multiple lenses/sills throughout lower crust but only a single lens is imaged directly beneath the innermost axial zone in prior seismic studies . Here, high-fidelity seismic data from the East Pacific Rise reveal series of reflections below the axial magma lens that we interpret as mid-lower crustal lenses. These deeper lenses are present between 9°20-57′N at variable two-way-travel-times, up to 4.6 s (~1.5 km beneath the axial magma lens), providing direct support for the sheeted sill model. From local changes in the amplitude and geometry of the events beneath a zone of recent volcanic eruption, we infer that melt drained from a lower lens contributed to the replenishment of the axial magma lens above and, perhaps, the eruption. The new data indicate that a multi-level sill complex is present beneath the East Pacific Rise that likely contributes to the formation of both the upper and lower crust.This research was supported by NSF awards OCE0327872 to J. C. M., S. M. C., OCE- 0327885 to J. P. C., and OCE0624401 to M. R. N.2015-04-1

Crustal thickness and Moho character of the fast-spreading East Pacific Rise from 9°42′N to 9°57′N from poststack-migrated 3-D MCS data

Author Posting. © American Geophysical Union, 2014. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 15 (2014): 634–657, doi:10.1002/2013GC005069.We computed crustal thickness (5740 ± 270 m) and mapped Moho reflection character using 3-D seismic data covering 658 km2 of the fast-spreading East Pacific Rise (EPR) from 9°42′N to 9°57′N. Moho reflections are imaged within ∼87% of the study area. Average crustal thickness varies little between large sections of the study area suggesting regionally uniform crustal production in the last ∼180 Ka. However, individual crustal thickness measurements differ by as much as 1.75 km indicating that the mantle melt delivery has not been uniform. Third-order, but not fourth-order ridge discontinuities are associated with changes in the Moho reflection character and/or near-axis crustal thickness. This suggests that the third-order segmentation is governed by melt distribution processes within the uppermost mantle while the fourth-order ridge segmentation arises from midcrustal to upper-crustal processes. In this light, we assign fourth-order ridge discontinuity status to the debated ridge segment boundary at ∼9°45′N and third-order status at ∼9°51.5′N to the ridge segment boundary previously interpreted as a fourth-order discontinuity. Our seismic results also suggest that the mechanism of lower-crustal accretion varies along the investigated section of the EPR but that the volume of melt delivered to the crust is mostly uniform. More efficient mantle melt extraction is inferred within the southern half of our survey area with greater proportion of the lower crust accreted from the axial magma lens than that for the northern half. This south-to-north variation in the crustal accretion style may be caused by interaction between the melt sources for the ridge and the Lamont seamounts.This research was supported by the National Science Foundation grants OCE0327872 to J. C. M., S. M. C., OCE327885 to J. P. C., OCE0624401 to M. R. N., and NSERC Discovery, CRC and CFI grants to M. R. N.2014-09-1

Variations in axial magma lens properties along the East Pacific Rise (9°30′N–10°00′N) from swath 3-D seismic imaging and 1-D waveform inversion

Author Posting. © American Geophysical Union, 2014. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Solid Earth 119 (2014): 2721–2744, doi:10.1002/2013JB010730.We use three-dimensional multistreamer seismic reflection data to investigate variations in axial magma lens (AML) physical properties along the East Pacific Rise between 9°30′N and 10°00′N. Using partial-offset stacks of P- and S-converted waves reflecting off the top of the AML, we image four 2–4 km long melt-rich sections spaced 5–10 km from each other. One-dimensional waveform inversion indicates that the AML in a melt-rich section is best modeled with a low Vp (2.95–3.23 km/s) and Vs (0.3–1.5 km/s), indicating >70% melt fraction. In contrast, the AML in a melt-poor section requires higher Vp (4.52–4.82 km/s) and Vs (2.0–3.0 km/s), which indicates <40% melt fraction. The thicknesses of the AML are constrained to be 8–32 m and 8–120 m at the melt-rich and -poor sites, respectively. Based on the AML melt-mush segmentation imaged in the area around the 2005–2006 eruption, we infer that the main source of this eruption was a 5 km long section of the AML between 9°48′N and 51′N. The eruption drained most of the melt in this section of the AML, leaving behind a large fraction of connected crystals. We estimate that during the 2005–2006 eruption, a total magma volume of 9–83 × 106 m3 was extracted from the AML, with a maximum of 71 × 106 m3 left unerupted in the crust as dikes. From this, we conclude that an eruption of similar dimensions to the 2005–2006, one would be needed with a frequency of years to decades in order to sustain the long-term average seafloor spreading rate at this location.This research was supported by NSF grants OCE-0327885 and OCE-0327872 through the RIDGE-2000 program.2014-10-2

Distribution of melt along the East Pacific Rise from 9°30′ to 10°N from an amplitude variation with angle of incidence (AVA) technique

Author Posting. © The Author(s), 2015. This article is posted here by permission of The Royal Astronomical Society for personal use, not for redistribution. The definitive version was published in Geophysical Journal International 203 (2015): 1-21, doi:10.1093/gji/ggv251.We examine along-axis variations in melt content of the axial magma lens (AML) beneath the fast-spreading East Pacific Rise (EPR) using an amplitude variation with angle of incidence (AVA) crossplotting method applied to multichannel seismic data acquired in 2008. The AVA crossplotting method, which has been developed for and, so far, applied for hydrocarbon prospection in sediments, is for the first time applied to a hardrock environment. We focus our analysis on 2-D data collected along the EPR axis from 9°29.8′N to 9°58.4′N, a region which encompasses the sites of two well-documented submarine volcanic eruptions (1991–1992 and 2005–2006). AVA crossplotting is performed for a ∼53 km length of the EPR spanning nine individual AML segments (ranging in length from ∼3.2 to 8.5 km) previously identified from the geometry of the AML and disruptions in continuity. Our detailed analyses conducted at 62.5 m interval show that within most of the analysed segments melt content varies at spatial scales much smaller (a few hundred of metres) than the length of the fine-scale AML segments, suggesting high heterogeneity in melt concentration. At the time of our survey, about 2 yr after the eruption, our results indicate that the three AML segments that directly underlie the 2005–2006 lava flow are on average mostly molten. However, detailed analysis at finer-scale intervals for these three segments reveals AML pockets (from >62.5 to 812.5 m long) with a low melt fraction. The longest such mushy section is centred beneath the main eruption site at ∼9°50.4′N, possibly reflecting a region of primary melt drainage during the 2005–2006 event. The complex geometry of fluid flow pathways within the crust above the AML and the different response times of fluid flow and venting to eruption and magma reservoir replenishment may contribute to the poor spatial correlation between incidence of hydrothermal vents and presence of highly molten AML. The presented results are an important step forward in our ability to resolve small-scale characteristics of the AML and recommend the AVA crossplotting as a tool for examining mid-ocean ridge magma-systems elsewhere.This research was supported by NSF awards OCE0327872 to J.C.M. and S.M.C., OCE-0327885 to J.P.C., and OCE0624401 to M.R.N

Recent advances in multichannel seismic imaging for academic research in deep oceanic environments

Author Posting. © The Oceanography Society, 2012. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 25, no. 1 (2012): 113–115, doi:10.5670/oceanog.2012.09.Academic research using marine multichannel seismic (MCS) methods to investigate processes related to Earth's oceanic crust has made substantial advances in the last decade. These advances were made possible by access to state-of-the-art MCS acquisition systems, and by development of data processing and modeling techniques that specifically deal with the particularities of oceanic crustal structure and the challenges of subseafloor imaging in the deep ocean. Among these methods, we highlight multistreamer three-dimensional (3D) imaging, streamer refraction tomography, synthetic ocean bottom experiments (SOBE), and time-lapse (4D) studies.The studies highlighted here were supported by NSF OCE grants 0327885, 0327872, 0621660, and 0826481

Physical Electronics

Contains reports on three research projects

Physical Electronics

Contains reports on three research projects