Biomarker characterisation and hydrous pyrolysis of bitumens from Tertiary volcanics, queen Charlotte islands, British Columbia, Canada

A number of bitumen samples have been recovered from vugs and fractures in outcropping Tertiary basalts of the Queen Charlotte Islands off the west coast of British Columbia, Canada. n-Alkanes and acyclic isoprenoids are not present and the polycyclic biomarker distribution of the four samples analyzed by GC and GC-MS has been altered. One sample contains no remaining recognizable biomarkers. Two bitumens were also obtained from Lower Jurassic potential source rocks, including one from the Sandilands Formation, which was considered previously to be the most likely source of the Tertiary bitumens. Although these two bitumens were also taken from outcrops, they are considerably less biodegraded. The Sandilands Formation bitumen contains 28, 30-bisnorhopanes and since these compounds were not detected in the Tertiary bitumens, there is no evidence from the initial results for a Sandilands Formation contribution to the hydrocarbons in the Tertiary basalts. The presence of 18α(H)-oleanane in the saturate fraction of two of the Tertiary bitumens from widely separated locations indicates that they are at least partially sourced from Tertiary organic matter.Because the distribution of biomarkers in some samples has been severely affected by biodegradation, the asphaltenes of the bitumens were hydrously-pyrolysed and the saturate fractions of the resulting pyrolysates analysed for possible additional information on the origin of the bitumens. The pyrolysates from the more degraded samples contain compounds not detected in the saturate fractions of the original bitumen and show some of the expected characteristics of the original non-degraded bitumen. However, the compounds most useful for correlation are not present in the pyrolysates apparently due to their non-incorporation into the kerogen macromolecule. Our results suggest that hydrous-pyrolysis of asphaltenes is of limited use in the correlation of biodegraded samples and in determining their origins.     

Effect of chemical affinity on feldspar hydrolysis rates in two natural weathering systems

Recent studies of alkali-feldspar hydrolysis kinetics have shown that, in the near-neutral pH range, weathering rates in natural systems are up to three orders of magnitude slower than laboratory rates. It has been hypothesized that decelerated rates may result from lower thermodynamic affinities for the hydrolysis reaction in natural systems than in laboratory systems. However, the chemical affinities for the feldspar hydrolysis reaction in two well-constrained natural systems are significantly higher than the threshold value at which affinity would exert detectable influences on the reaction rates. Thus, the hypothesis is rejected, and closer proximity to thermodynamic equilibrium in natural weathering systems does not account for the observed discrepancy between natural and laboratory rates of feldspar hydrolysis. Differences in feldspar weathering rates between natural and laboratory systems are most likely due to a combination of experimental preparation artifacts, loss of reactive surface to the formation of etch pits in naturally weathered feldspars, and inhomogeneous access of reactive fluids to those surfaces.     

Two-dimensional kinematic and rheological modeling of the 1912 pyroclastic flow,Katmai, Alaska

Pyroclastic flow emplacement is strongly influenced by eruption column height. A surface along which kinetic energy is zero theoretically connects the loci of eruption column collapse with all coeval ignimbrite termini. This surface is reconstructed as a two-dimensional energy line for the 1912 Katmai pyroclastic flow in the Valley of Ten Thousand Smokes from mapped flow termini and the runup of the ignimbrite onto obstructions and through passes. Extrapolation of the energy line to the vicinity of the source vent at Novarupta suggests the eruption column which generated the ignimbrite eruption was approximately 425 m high. The 1912 pyroclastic flow travelled about 25 km downvalley. Empirical velocity data calculated from runup elevations and surveyed centrifugal superelevations indicate initial velocities near Novarupta were greater than 79–88 m s^–1. The flow progressively decelerated and was travelling only 2–8 m s^–1 when it crossed a moraine 16 km downvalley. The constant slope of the energy line away from Novarupta suggests the flow was systematically slowed by internal and basal friction. Using a simple physical model to calculate flow velocities and a constant kinetic friction coefficient (Heim coefficient) of 0.04 derived from the reconstructed energy line, the flow is estimated to have decelerated at an average rate of –0.16 m s^–2 and to have taken approximately 9.5 minutes to travel 25 km down the Valley of Ten Thousand Smokes. The shear strength of the flowing ignimbrite at the moraine was approximately 0.5 kPa, and its Bingham viscosity when it crossed the moraine was 3.5 × 10³ P. If the flow was Newtonian, its viscosity was 4.2 × 10³ P. Reynolds and Froude numbers at the moraine were only 41–62 and 0.84–1.04, respectively, indicating laminar, subcritical flow.     

Chemistry of alkali extraction of brown coals—I. Kinetics, characterisation and implications to coalification

Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state ¹³C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.     

Fouling of floating plastic debris under Biscayne Bay exposure conditions

Six plastic/rubber materials commonly encountered in marine debris and beach litter were studied under Biscayne Bay (Florida, USA) exposure conditions to determine the effect of fouling on buoyancy. Studies under restricted floating, and restricted submerged exposure conditions suggest that most plastic samples undergo fouling to an extent to cause the sample to be negatively buoyant in sea water. Rapid defouling of the submerged fouled samples was observed. The findings suggest that free-floating plastics at sea may, under certain conditions, undergo fouling-induced sinking followed by resurfacing as floating debris.     

Temporal variation of tropical cyclones in the North Atlantic Basin

A total of 269 tropical storms and hurricanes originated in the North Atlantic basin from 1960–1989. Of these, 76 made landfall on the continental United states. This study divides the 76 tropical storms into their month of formation. Seasonal shifts in the principal areas of tropical cyclone formation over the Atlantic basin have been recognized for many decades. The results of the study suggest that the early and late season tropical cyclones develop in areas which are first affected by the position of the sun, resulting in an increase in water temperatures. These cyclones normally make landfall along the Gulf Coast and usually are of low intensity. Formation areas shift eastward in mid-summer with a slight increase in intensity. By late August and early September, the formation areas have extended to the Cape Verde Islands. These storms tend to strike the east coast of the US and are normally more intense. By the end of the hurricane season, the primary formation area has shifted back to the Gulf of Mexico, with low intensity storms affecting the Gulf Coast.