Chlorine initiated oxidation studies of hydrochlorofluorocarbons: Results for HCFC-123 (CF3CHCl2) and HCFC-141b (CFCl2CH3)

Oxidation reactions of the proposed CFC substitutes HCFC-123 (CF₃CHCl₂) and HCFC-141b (CFCl₂CH₃) have been studied in the laboratory using long-path Fourier transform infrared spectroscopy. The air oxidation of the HCFCs was initiated by the photolysis of Cl₂ forming Cl atoms that abstract H atoms from the HCFC. CF₃C(O)Cl was the only carbon containing compound observed in the infrared spectrum of the products of the HCFC-123/Cl₂ irradiations and its yield was approximately one. The product data are consistent with formation of CF₃C(O)Cl by Cl elimination of the intermediate halogenated alkoxy radical CF₃CCl₂O. The Cl-initiated oxidation of HCFC-141b led to the formation of CO and C(O)FCl. The product data are consistent with a 1 : 1 relationship between C(O)FCl formed and HCFC-141b reacted. Product data were compatible with both decomposition by cleavage of the C–C bond of the radical CFCl₂CH₂O leading to the prompt generation of C(O)FCl and reaction of the radical with O₂ forming the two carbon halogenated aldehyde CFCl₂CH(O), which in the presence of Cl was likely oxidized to C(O)FCl. An approximate method was developed in which the ratio was extracted from analysis of the time evolution of HCFC-141b, C(O)FCl, and CO. The data suggest that the contributions are comparable.     

Clay mineralogy of Gulf of Papua Shelf and Pandora Trough deposits constrains sediment routing during the last sea-level cycle

The Gulf of Papua inner mid-shelf clinothem and lowstand deposits in Pandora Trough record sediment source and routing through the last sea-level cycle on 20 kyr cycles. Clay mineralogy tracked dispersal of sediment from the two types of rivers (wide versus narrow floodplains) to constrain the contributions of river systems to the Gulf of Papua clinothem and Pandora Trough deposits. Fly River sediment has higher illite:smectite than clays from the small mountainous rivers (Bamu, Turama, Kikori and Purari rivers) that drain regions with more limestones. X-ray diffraction shows high illite:smectite proximal to the Fly River delta that decrease towards the north-east. Downcore mineralogy of inner mid-shelf cores reveals that the largest shifts in illite:smectite correspond to changes in sediment units. The relict clinothem emplaced on the Gulf of Papua shelf during Marine Isotope Stage 3 has lower illite:smectite than the Holocene clinothem that has been building since 2 ka and the Marine Isotope Stage 5a relict clinothem. In the inner mid-shelf, downcore decreases in illite:smectite during Marine Isotope Stage 3 suggest that this region received less clay from the Fly River and more contributions from small mountainous rivers. During Marine Isotope Stage 3, the exposed physiography and narrower shelf in this region may have deflected Fly River sediment more south-eastward, where it bypassed the inner shelf via the Kiwai, Purutu and Umuda valleys and was deposited in the Pandora Trough. The Fly River may have been more susceptible to valley incision because of its limited shelf accommodation and higher ratio of water to sediment discharge. Such bypass of the inner mid-shelf by Fly River sediment during the Marine Isotope Stage 2 sea-level lowstand is recorded in Pandora Trough deposits with high illite:smectite ratios. Inner mid-shelf clinothems with compositional shifts on the order of 20 kyr may be influenced by shelf physiography, accommodation and the variable incision by small and large rivers.     

Runoff sensitivity to snow depletion curve representation within a continental scale hydrologic model

The spatial variability of snow water equivalent (SWE) can exert a strong influence on the timing and magnitude of snowmelt delivery to a watershed. Therefore, the representation of sub-grid or sub-watershed snow variability in hydrologic models is important for accurately simulating snowmelt dynamics and runoff response. The U.S. Geological Survey National Hydrologic Model infrastructure with the precipitation-runoff modelling system (NHM-PRMS) represents the sub-grid variability of SWE with snow depletion curves (SDCs), which relate snow-covered area to watershed-mean SWE during the snowmelt period. The main objective of this research was to evaluate the sensitivity of simulated runoff to SDC representation within the NHM-PRMS across the continental United States (CONUS). SDCs for the model experiment were derived assuming a range of SWE coefficient of variation values and a lognormal probability distribution function. The NHM-PRMS was simulated at a daily time step for each SDC over a 14-year period. Results highlight that increasing the sub-grid snow variability (by changing the SDC) resulted in a consistently slower snowmelt rate and longer snowmelt duration when averaged across the hydrologic response unit scale. Simulated runoff was also found to be sensitive to SDC representation, as decreases in simulated snowmelt rate by 1 mm day⁻¹ resulted in decreases in runoff ratio by 1.8% on average in snow-dominated regions of the CONUS. Simulated decreases in runoff associated with slower snowmelt rates were approximately inversely proportional to increases in simulated evapotranspiration. High snow persistence and peak SWE:annual precipitation combined with a water-limited dryness index was associated with the greatest runoff sensitivity to changing snowmelt. Results from this study highlight the importance of carefully parameterizing SDCs for hydrologic modelling. Furthermore, improving model representation of snowmelt input variability and its relation to runoff generation processes is shown to be an important consideration for future modelling applications.     

Choosing the coherent integration time for Kalman filter-based carrier-phase tracking of GNSS signals

Carrier phase–based positioning using Global Navigation Satellite System (GNSS) signals can provide centimeter-level accuracy; however, to do so requires robust, continuous tracking of the phase of the received signal. The phase-locked loop is typically the weakest link in GNSS signal processing, with frequent cycle slips and loss of lock occurring at lower signal-to-noise ratios. One way to improve the signal-to-noise ratio is to increase the coherent integration time; however doing so reduces the loop update rate, thereby degrading performance. This paper investigates this trade-off between sensitivity and loop update rate by investigation of the Kalman filter-based tracking loop. It is shown that it is possible to choose an optimal integration time for a given application. A relatively straightforward procedure is given to determine this optimal value. The results are confirmed through real-time kinematic processing of live satellite signals.     

Geobarometry of low-temperature eclogites: applications of isothermal pressure-activity calculations

Estimation of metamorphic pressures in low temperature eclogite (Type C) is difficult because of the high variance mineral assemblages and problems in geothermometry, solution properties of low-temperature omphacite, and the thermodynamic properties of clinozoisite. We have considered equilibria in the CaO–FeO–MgO–TiO₂–Al₂O₃–SiO₂–H₂O (CFMTASH) system involving the phase components, quartz, rutile, kyanite, ilmenite, almandine, pyrope, grossular, clinozoisite, sphene, diopside, and H₂O-fluid There are four linearly independent equilibria involving the phase components in this system. Because kyanite can crystallize as a nearly pure phase, the lack of kyanite in a rock indicates that a _Al2SiO5 is<1.0. If we can estimate temperature independently, we can solve for a _Al2SiO5 and pressure by using two of the equilibria in isothermal pressure-activity diagrams. We have applied this approach to eclogites from New Caledonia and from southwestern Oregon. For the New Caledonia eclogites, calculated pressures range from 11.2 to 13.6 kbar at 500°C, and are consistent with the minimum pressures based upon the presence of jadeitic pyroxene+quartz and the lack of stable albite. Oregon eclogites come from different tectonic blocks and calculated minimum pressures of 11–12 kbar are based upon the presence of jadeitic pyroxene+rutile+garnet and lack of stable albite and ilmenite at reduced values of a _SiO2 (0.7–0.9).     

Fuel use and greenhouse gas emission implications of fisheries management: the case of the new england atlantic herring fishery

Commercial fisheries are heavily dependent upon the combustion of fossil fuels and as such contribute to increased atmospheric concentrations of greenhouse gases and the concomitant impact on the world's climate. The fuel use and greenhouse gas intensity of a fishery is a function of several variables. One that has not been previously investigated is the role of fisheries management. Using historical gear-specific fuel use and landings data, we employ scenarios to examine the potential impact that recent changes in the management of the New England fishery for Atlantic herring (Clupea harengus) may have on fishery-related fuel use and greenhouse gas emissions. Specifically, we consider the direct effect of the seasonal ban of midwater trawling in favor of purse seine and fixed gears within Atlantic herring fishing Area 1A. We also evaluate the indirect effect of reductions to the Area 1A total allowable catch of Atlantic herring on the regional supply of bait and the resulting potential need to import bait herring from Canada. Our results indicate that because of the five-fold lower fuel intensity of purse seining, relative to midwater trawling (21 L/ton versus 108-118 L/ton), the seasonal ban on midwater trawling has the potential to markedly reduce overall fuel use and greenhouse gas emissions associated with the herring fishery. These results indicate that management decisions can strongly influence energy demands and resulting greenhouse gas emissions of fisheries. We urge those involved with fisheries management to take this into account when developing policy and management measures.     

The motion of a deep-sea remotely operated vehicle system: Part 1: Motion observations

Rapid and high-resolution motion and tension measurements were made of a caged deep-sea remotely operated vehicle (ROV) system. Simultaneous measurements were made of all six components of motion at the cage and ship A-frame and of the tension in the tether at the ship. Data were collected for cage depths of 0–1765 m. The most significant forcing was in the wave-frequency band (0.1–0.25 Hz) and accounted for over 90% of the variance of vertical acceleration. The vertical acceleration of the cage lagged the acceleration of the A-frame by up to 1.9 s and its variance was larger by up to a factor 2.2. For moderate displacements of the A-frame (≤2 m), the system is only weakly non-linear because the harmonics (3rd and 5th) of the vertical acceleration of the cage account for less than 2% of the total variance. The system is essentially one-dimensional because only the vertical motion of the cage and the vertical motion of the A-frame were coherent, while horizontal motions of the cage were weak and incoherent with any component of motion of the A-frame. The natural frequency of the system is 0.22 Hz at 1730 m, and we estimate that it is within the waveband for depths between 1450 m and the full operating depth of 5000 m.Large vertical excursions of the A-frame produce momentary slack in the tether near the cage. Retensioning results in snap loads with vertical accelerations of 0.5 gravity. Large rates of change of tension and vertical acceleration first occur at the cage during its downward motion and propagate to the surface with the characteristic speed (3870 m s⁻¹) of tensile waves for the tether. Six echoes are clearly detectable at both ends of the tether, and their pattern is extremely repeatable in different snap loads. Due to misalignment of the tether termination with the centres of mass and buoyancy, the cage pitches by up 14° during a snap. The resulting small radius of curvature poses the greatest stress on the tether.     

Design of a prototype ocean current turbine—Part I: mathematical modeling and dynamics simulation

The “C-Plane” is a submerged variable depth ocean current turbine that is tethered to the sea floor and uses sustained ocean currents to produce electricity. As part of the development of a $\frac{1}{30}$th scale physical model of the C-Plane, a mathematical model and dynamics simulation of the prototype was developed and is presented in this paper. This three-dimensional mathematical model represents the C-Plane as a rigid body with moveable control surfaces that is moored with three linear elastic cable elements. Gravitational, buoyancy, hydrodynamic, cable, gyroscopic, and inertial forces are included and a PC-based dynamics simulation is created. The simulation demonstrates that the C-Plane is stable and capable of changing depth in all expected operating conditions. The C-Plane prototype can fly level from a height of 3 to 6 m using the configuration suggested in this paper. The maximum ascent rates of the C-Plane with a water speed of 0.3 m/s are 0.015 m/s when the pitch is fixed at 0° and 0.030 m/s when the pitch is fixed at 4°. The maximum descent rates of the C-Plane are 0.018 m/s when the pitch is held at 0° and 0.031 m/s if the pitch is held at −4°.