Combining advanced NMR techniques with ultrahigh resolution mass spectrometry: A new strategy for molecular scale characterization of macromolecular components of soil and sedimentary organic matter     

Junyan Zhong  Rachel L. SleighterElodie Salmon  Georgina A. McKeePatrick G. Hatcher 《Organic Geochemistry》2011,42(8):903-916

Molecular level characterization of complex biopolymers in nature is a key element to understanding the composition of natural organic matter (NOM) and fossil organic matter formation, such as kerogen and coal. Characterization of such geopolymers is difficult due to their heterogeneity and insolubility in common aqueous or organic solvents. Here, a strategy for extracting a representative sample is presented using the combined techniques of nuclear magnetic resonance (NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) for chemical analysis and characterization of NOM. A variety of NOM samples (wood, kerogen, bitumen, whole sediments) are shown as examples for implementing the strategy, which include solvent extractions using pyridine. For most samples, the extracts are confirmed to be chemically representative of the insoluble solid, by comparing the liquids NMR spectrum of the extract to that of the whole, unfractionated NOM utilizing high resolution magic angle spinning (HRMAS) NMR. To assist in unambiguous peak assignment, a technique for post acquisition spectral denoising, using wavelet transformation (WT), is also employed on the 1D and 2D NMR spectra. The findings from the NMR data lay a foundation for the subsequent electrospray ionization FTICR-MS analysis of the pyridine extracts, since this instrument has the limitation of only analyzing liquid samples. The FTICR-MS analyses can, therefore, be used to molecularly represent the structural components of the NOM. Various compositional insights have been obtained on these samples, indicating the efficacy of the analytical techniques used.  相似文献   

Modelling tidal current turbine wakes using a coupled RANS-BEMT approach as a tool for analysing power capture of arrays of turbines     

Stephen R. Turnock  Alexander B. Phillips  Joe Banks  Rachel Nicholls-Lee 《Ocean Engineering》2011,38(11-12):1300-1307

An improved method is developed to couple an inner domain solution of the blade element momentum theory with an outer domain solution of the Reynolds averaged Navier Stokes equations for evaluating performance of tidal current turbines. A mesh sensitivity study shows that a mesh of at least 6 M cells with at least 40% of these within the turbine wake is required to ensure satisfactory convergence of the velocity deficit. In addition to the usually applied axial momentum source terms, angular momentum and turbulence intensity source terms are shown to be required to model the near wake evolution. Three different lateral turbine spacing of 2, 4 and 6 turbine diameters are used to demonstrate the influence of the effective channel blockage on the velocity distribution in the turbine bypass region, the rate of spread of the wake and the recovery of velocity distribution. A final study shows that for a fixed number of turbines minimising the lateral spacing within each row, with a small number of staggered rows spaced as longitudinally as far apart as practical, is the most effective strategy for energy capture.  相似文献   

Late Devonian OIB alkaline gabbro in the Yarlung Zangbo Suture Zone: Remnants of the Paleo-Tethys?     

Jingen Dai  Chengshan Wang  Réjean Hébert  Yalin Li  Hanting Zhong  Raoult Guillaume  Rachel Bezard  Yushuai Wei 《Gondwana Research》2011,19(1):232-243

The Yarlung Zangbo Suture Zone (YZSZ) is believed to be composed of material largely derived from the destruction of the Neo-Tethys that occurred from early Mesozoic to early Cenozoic. We report here geochronological and petrological data obtained for newly discovered alkaline gabbro blocks embedded in a mélange zone of the western YZSZ. Single zircon U–Pb analyses from one representative gabbro sample by SIMS (Secondary Ion Mass Spectrometry) yielded a combined crystallization age of about 363.7 ± 1.7 Ma (1σ). In situ Hf isotopic analyses yielded ε_Hf(t) values of + 2.6 to + 5.5, suggesting an enriched mantle source. All of the gabbro samples show typical Ocean Island Basalt (OIB) affinity with little or no continental crust contamination. They also display strong geochemical similarities with the Hawaii basalts and the Xigaze seamount basalts suggestive of their intra-oceanic setting. These observations, in combination with the Early Carboniferous layered gabbros reported at Luobusa, indicate that these rocks could represent remnants of the Paleo-Tethys. We propose that a branch ocean separating the Western Qiangtang terrane and the Lhasa terrane from the Gondwana continent might have been present during the Late Devonian and the Early Carboniferous, providing new constrains on the configuration of Paleo-Tethys in Tibetan Plateau during early Late Paleozoic.  相似文献   

The chemical changes of DOM from black waters to coastal marine waters by HPLC combined with ultrahigh resolution mass spectrometry     

Zhanfei Liu  Rachel L. Sleighter  Junyan Zhong  Patrick G. Hatcher 《Estuarine, Coastal and Shelf Science》2011

How dissolved organic matter (DOM) undergoes chemical changes during its transit from river to ocean remains a challenge due to its complex structure. In this study, DOM along a river transect from black waters to marine waters is characterized using an offline combination of reversed-phase high performance liquid chromatography (RP-HPLC) coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS), as well as tandem ESI-FTICR-MS. In addition, a water extract from degraded wood that mainly consists of lignins is used for comparison to the DOM from this transect. The HPLC chromatograms of all DOM samples and the wood extract show two major well-separated components; one is hydrophilic and the other is hydrophobic, based on their elution order from the C₁₈ column. From the FTICR-MS analysis of the HPLC fractions, the hydrophilic components mainly contain low molecular weight compounds (less than 400 Da), while the hydrophobic fractions contain the vast majority of compounds of the bulk C₁₈ extracted DOM. The wood extract and the DOM samples from the transect of black waters to coastal marine waters show strikingly similar HPLC chromatograms, and the FTICR-MS analysis further indicates that a large fraction of molecular formulas from these samples are the same, existing as lignin-like compounds. Tandem mass spectrometry experiments show that several representative molecules from the lignin-like compounds have similar functional group losses and fragmentation patterns, consistent with modified lignin structural entities in the wood extract and these DOM samples. Taken together, these data suggest that lignin-derived compounds may survive the transit from the river to the coastal ocean and can accumulate there because of their refractory nature.  相似文献   

Influence of seepage undercutting on the stability of root‐reinforced streambanks     

Rachel M. Cancienne  Garey A. Fox  Andrew Simon 《地球表面变化过程与地形》2008,33(11):1769-1786

Several mechanisms contribute to streambank failure including fluvial toe undercutting, reduced soil shear strength by increased soil pore‐water pressure, and seepage erosion. Recent research has suggested that seepage erosion of noncohesive soil layers undercutting the banks may play an equivalent role in streambank failure to increased soil pore‐water pressure. However, this past research has primarily been limited to laboratory studies of non‐vegetated banks. The objective of this research was to utilize the Bank Stability and Toe Erosion Model (BSTEM) in order to determine the importance of seepage undercutting relative to bank shear strength, bank angle, soil pore‐water pressure, and root reinforcement. The BSTEM simulated two streambanks: Little Topashaw Creek and Goodwin Creek in northern Mississippi. Simulations included three bank angles (70° to 90°), four pore‐water pressure distributions (unsaturated, two partially saturated cases, and fully saturated), six distances of undercutting (0 to 40 cm), and 13 different vegetation conditions (root cohesions from 0·0 to 15·0 kPa). A relative sensitivity analysis suggested that BSTEM was approximately three to four times more sensitive to water table position than root cohesion or depth of seepage undercutting. Seepage undercutting becomes a prominent bank failure mechanism on unsaturated to partially saturated streambanks with root reinforcement, even with undercutting distances as small as 20 cm. Consideration of seepage undercutting is less important under conditions of partially to fully saturated soil pore‐water conditions. The distance at which instability by undercutting became equivalent to instability by increased soil pore‐water pressure decreased as root reinforcement increased, with values typically ranging between 20 and 40 cm at Little Topashaw Creek and between 20 and 55 cm at Goodwin Creek. This research depicts the baseline conditions at which seepage undercutting of vegetated streambanks needs to be considered for bank stability analyses. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

Phosphorus sources and demand during summer in a eutrophic lake     

Amy M. Kamarainen  Rachel M. Penczykowski  Matthew C. Van de Bogert  Paul C. Hanson  Stephen R. Carpenter 《Aquatic Sciences - Research Across Boundaries》2009,71(2):214-227

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Hydrogeology of a coal-seam gas exploration area, southeastern British Columbia, Canada: Part 1. Groundwater flow systems     

S. Harrison  J. Molson  H. Abercrombie  J. Barker  D. Rudolph  R. Aravena 《Hydrogeology Journal》2000,8(6):608-622

Discovery of high contents of methane gas in coals of the Mist Mountain Formation in the Elk River valley, southeastern British Columbia, Canada, has led to increased exploration activity for coal-seam gas (CSG). CSG production requires groundwater abstraction to depressurize the coal beds and to facilitate methane flow to the production wells. Groundwater abstraction will have hydrodynamic effects on the flow system, and an understanding of the groundwater flow system is needed to evaluate these effects. The purpose of this paper is to describe the groundwater flow system in the area by means of a groundwater flow model and interpretation of hydrochemical and isotopic analyses of groundwater and surface water. Groundwater flow for the Weary Creek exploration area is modeled in two vertical sections. The model domains, based on classic upland–lowland conceptual flow models, are approximately 10,000 m long and 4,000 m deep. Each consists of a fixed water-table boundary and no-flow boundaries along the traces of major faults. Steady-state groundwater flow is calibrated to hydraulic-head, streamflow, and groundwater-recharge data. Simulated steady-state velocity fields define regional and local flow components consistent with the conceptual model. The results are consistent with regional trends in δ²H, δ¹⁸O, tritium, and TDS, which define two distinct groundwater groups (A and B) and a third of intermediate composition. An active, shallow, local flow component (group A) is recharged in beds cropping out along subdued ridges; this component discharges as seeps along lower and mid-slope positions in the southern part of the study area. The waters are tritiated, relatively enriched in δ²H and δ¹⁸O, and have low TDS. A deeper regional flow component (group B), which originates at a higher altitude and which discharges to the Elk River valley bottom, is characterized by non-tritiated groundwater with relatively depleted δ²H and δ¹⁸O, and higher TDS. Groundwater contributes less than 10% of the total direct flow to the Elk River, as indicated by flow measurements and by the absence of group A and group B characteristics in the river water. Thus it is hypothesized that groundwater extraction during CSG production will have little impact on the river. The groundwater flow model developed in this work is used in a companion paper to further test this hypothesis. Electronic Publication  相似文献   

Geophysical and geochemical constraints on the age and paleoclimate implications of Holocene lacustrine cores from the Andes of central Chile          下载免费PDF全文

Rachel J. Tiner  Robert M. Negrini  Jose L. Antinao  Eric McDonald  Antonio Maldonado 《第四纪科学杂志》2018,33(2):150-165

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Pyrolysis of modern wetland sediment: extracting climate records from fens in the Uinta Mountains and Fish Lake Plateau,Utah, USA     

Samuel M. Hudson  Samuel A. Hillam  Joel Barker  Stephen T. Nelson  Kevin A. Rey 《Boreas: An International Journal of Quaternary Research》2019,48(3):810-824

Rock‐Eval pyrolysis provides a quick, relatively inexpensive means of characterizing organic‐rich strata, and has been used for decades to understand global petroleum systems. Although designed to characterize ancient kerogens, pyrolysis is increasingly being used to understand Holocene systems as well. The ability of this technique to distinguish between types of preserved organic matter is useful in characterizing climatic evolution, particularly in systems sensitive to climatic fluctuation such as isolated fens and bogs. Cores collected from the Tokewanna and Garden Basin Cattail fens in central/eastern Utah exhibit variability of organic source, with the mixture of terrestrial and algal sources varying through time, as shown through the hydrogen index (HI) and oxygen index pyrolysis parameters. A sediment core was collected at each fen, and 176 samples were taken from the cores at 6‐cm intervals. Total organic carbon (TOC) for all samples ranges from 1.3 to 44.2%, with an average of 18.2% TOC. Samples range from 84 to 687 HI, equivalent to Type I (lacustrine algal) to Type III (terrestrial) organic material (OM). Variability in HI response represents mixing of the two OM sources, and the relative amount of aqueous organic input can be estimated through time based on age‐calibrated HI curves at the two sites. The balance of organic input serves as an accurate, high‐resolution proxy for climate, and calibration with palynological data near both sites confirms patterns shown by pyrolysis, showing the utility of this method in quickly, affordably and accurately characterizing Holocene sediments for use in understanding palaeoclimate.  相似文献   

Comparison of ground-based and Viking Orbiter measurements of Martian water vapor: Variability of the seasonal cycle     

Bruce M. Jakosky  Edwin S. Barker 《Icarus》1984,57(3):322-334

Earth-based observations of Mars atmospheric water vapor, made from McDonald Observatory, are presented for the 1975–1976, 1977–1978, and 1983 apparitions. Comparisons are made with near-simultaneous spacecraft measurements made from the Viking Orbiter MarsAtmospheric Water Detection experiment during 1976–1978 and with previous Earth-based measurements (made since 1964). Differences occur between the behavior in the different years, and may be related to the Mars climate. Measurements during the southern summer in 1969 indicate a factor of three times as much water as is present at this same season in other years.This difference may have resulted from the sublimation of water from the south polar residual cap upon removal of most or all of the CO₂ ice present; sublimation of all the CO₂ ice during some years could be a result of a greater thermal load being placed on the cap due to the presence of differing amounts of atmospheric dust. If substantiated, the water vapor variability will turn out to be a very sensitive indicator of yearly variability in the Martian climate.  相似文献