Gas hydrate systems at Hydrate Ridge offshore Oregon inferred from molecular and isotopic properties of hydrate-bound and void gases

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C₂₊ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO₂ and H₂S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.     

Solution mechanisms of H2O in depolymerized peralkaline melts

Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na₂O-SiO₂-H₂O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂X_H2O, decreases with increasing total water content. At low water contents, the influence of H₂O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q⁴-species to form Q³ and Q² species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q³-species react with water to form Q²-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published ¹H and ²⁹Si MAS NMR and ¹H-²⁹Si cross polarization NMR data.     

Late Quaternary sea‐level change and evolution of Belfast Lough,Northern Ireland: new offshore evidence and implications for sea‐level reconstruction

The interplay of eustatic and isostatic factors causes complex relative sea‐level (RSL) histories, particularly in paraglacial settings. In this context the past record of RSL is important in understanding ice‐sheet history, earth rheology and resulting glacio‐isostatic adjustment. Field data to develop sea‐level reconstructions are often limited to shallow depths and uncertainty exists as to the veracity of modelled sea‐level curves. We use seismic stratigraphy, 39 vibrocores and 26 radiocarbon dates to investigate the deglacial history of Belfast Lough, Northern Ireland, and reconstruct past RSL. A typical sequence of till, glacimarine and Holocene sediments is preserved. Two sea‐level lowstands (both max. ?40 m) are recorded at c. 13.5 and 11.5k cal a bp . Each is followed by a rapid transgression and subsequent periods of RSL stability. The first transgression coincides temporally with a late stage of Meltwater Pulse 1a and the RSL stability occurred between c. 13.0 and c. 12.2k cal a bp (Younger Dryas). The second still/slowstand occurred between c. 10.3 and c. 11.5k cal a bp . Our data provide constraints on the direction and timing of RSL change during deglaciation. Application of the Depth of Closure concept adds an error term to sea‐level reconstructions based on seismic stratigraphic reconstructions.     

Vertical vibration of a rigid strip footing on viscoelastic half-space

This paper presents an analytical method for modeling the dynamic response of a rigid strip footing subjected to vertical-only loads. The footing is assumed to rest on the surface of a viscoelastic half-space; therefore, effects of hysteretic soil damping on the impedance of the foundation and the generated ground vibrations are considered in the solution. To solve the mixed boundary value problem, we use the Fourier transform to cast a pair of dual integral equations providing contact stresses, which are solved by means of Jacobi orthogonal polynomials. The resulting soil and footing displacements and stresses are obtained by means of the Fourier inverse transform. The solution provides more realistic estimates of footing impedance, compared to existing solutions for elastic soil, as well as of the attenuation of ground vibrations with distance of the footing. The latter is important for the estimation of machine vibration effects on nearby structures and installations.     

A long‐term study of stable isotopes as tracers of processes governing water flow and quality in a lowland river basin: the upper Thames,UK

A long‐term study of O, H and C stable isotopes has been undertaken on river waters across the 7000‐km² upper Thames lowland river basin in the southern UK. During the period, flow conditions ranged from drought to flood. A 10‐year monthly record (2003–2012) of the main River Thames showed a maximum variation of 3‰ (δ¹⁸O) and 20‰ (δ²H), although interannual average values varied little around a mean of –6.5‰ (δ¹⁸O) and –44‰ (δ²H). A δ²H/δ¹⁸O slope of 5.3 suggested a degree of evaporative enrichment, consistent with derivation from local rainfall with a weighted mean of –7.2‰ (δ¹⁸O) and –48‰ (δ²H) for the period. A tendency towards isotopic depletion of the river with increasing flow rate was noted, but at very high flows (>100 m³/s), a reversion to the mean was interpreted as the displacement of bank storage by rising groundwater levels (corroborated by measurements of specific electrical conductivity). A shorter quarterly study (October 2011–April 2013) of isotope variations in 15 tributaries with varying geology revealed different responses to evaporation, with a well‐correlated inverse relationship between Δ¹⁸O and baseflow index for most of the rivers. A comparison with aquifer waters in the basin showed that even at low flow, rivers rarely consist solely of isotopically unmodified groundwater. Long‐term monitoring (2003–2007) of carbon stable isotopes in dissolved inorganic carbon (DIC) in the Thames revealed a complex interplay between respiration, photosynthesis and evasion, but with a mean interannual δ¹³C‐DIC value of –14.8 ± 0.5‰, exchange with atmospheric carbon could be ruled out. Quarterly monitoring of the tributaries (October 2011–April 2013) indicated that in addition to the aforementioned factors, river flow variations and catchment characteristics were likely to affect δ¹³C‐DIC. Comparison with basin groundwaters of different alkalinity and δ¹³C‐DIC values showed that the origin of river baseflow is usually obscured. The findings show that long‐term monitoring of environmental tracers can help to improve the understanding of how lowland river catchments function. Copyright © NERC 2015. Hydrological Processes © 2015 John Wiley & Sons, Ltd.     

Combining two filter paper‐based analytical methods to monitor temporal variations in the geochemical properties of fluvial suspended particulate matter

Many of the commonly used analytical techniques for assessing the properties of fluvial suspended particulate matter (SPM) are neither cost effective nor time efficient, making them prohibitive to long‐term high‐resolution monitoring. We present an in‐depth methodology utilizing two types of spectroscopy which, when combined with automatic water samplers, can generate accurate, high‐temporal resolution SPM geochemistry data, inexpensively and semi‐destructively, directly from sediment covered filter papers. A combined X‐ray fluorescence spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy approach is developed to estimate concentrations for a range of elements (Al, Ca, Ce, Fe, K, Mg, Mn, Na, P, Si, Ti) and compounds (organic carbon, Al_dithionate, Al_oxalate, Fe_dithionate, and Fe_oxalate) within SPM trapped on quartz fibre filters at masses as low as 3 mg. Calibration models with small prediction errors are derived, along with mass correction factor models to account for variations in retained SPM mass. Spectral pre‐processing methods are shown to enhance the reproducibility of results for some compounds, and the importance of filter paper selection and homogeneous sample preparation in minimizing spectral interference is emphasized. The geochemical signal from sediment covered filter papers is demonstrated to be time stable enabling samples to be stored for several weeks prior to analysis. Example results obtained during a heavy precipitation event in October 2012 demonstrate the methodology presented here has considerable potential to be utilized for high‐resolution monitoring of SPM geochemistry under a range of in‐stream hydrological conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Calibration of paired watersheds: Utility of moving sums in presence of externalities

Historically, paired watershed studies have been used to quantify the hydrological effects of land use and management practices by concurrently monitoring 2 similar watersheds during calibration (pretreatment) and post‐treatment periods. This study characterizes seasonal water table and flow response to rainfall during the calibration period and tests a change detection technique of moving sums of recursive residuals (MOSUM) to select calibration periods for each control–treatment watershed pair when the regression coefficients for daily water table elevation were most stable to minimize regression model uncertainty. The control and treatment watersheds were 1 watershed of 3–4‐year‐old intensely managed loblolly pine (Pinus taeda L.) with natural understory, 1 watershed of 3–4‐year‐old loblolly pine intercropped with switchgrass (Panicum virgatum), 1 watershed of 14–15‐year‐old thinned loblolly pine with natural understory (control), and 1 watershed of switchgrass only. The study period spanned from 2009 to 2012. Silvicultural operational practices during this period acted as external factors, potentially shifting hydrologic calibration relationships between control and treatment watersheds. MOSUM results indicated significant changes in regression parameters due to silvicultural operations and were used to identify stable relationships for water table elevation. None of the calibration relationships developed using this method were significantly different from the classical calibration relationship based on published historical data. We attribute that to the similarity of historical and 2010–2012 leaf area index on control and treatment watersheds as moderated by the emergent vegetation. Although the MOSUM approach does not eliminate the need for true calibration data or replace the classic paired watershed approach, our results show that it may be an effective alternative approach when true data are unavailable, as it minimizes the impacts of external disturbances other than the treatment of interest.