Hydropyrolysis of algae, bacteria, archaea and lake sediments; insights into the origin of nitrogen compounds in petroleum

Nitrogen compounds are ubiquitous in fossil fuels and yet our understanding of their origins in the geosphere is limited. In this study, high hydrogen pressure pyrolysis was performed on sample material representing potential contributors to sedimentary organic matter (algae, bacteria and archaea) and sediments representing early diagenetic accumulations from Lake Pollen (Norway) and Priest Pot (UK). Previous workers demonstrated the structurally conservative nature of high hydrogen pressure pyrolysis in that the technique maximizes the yields of covalently bound hydrocarbon biomarkers from organic matter without adversely affecting their stereochemistry (Love et al., 1995). Release of covalently bound biomarkers in high yields from kerogen via catalytic hydropyrolysis. In this study, the types and distributions of organic nitrogen compounds in the hydropyrolysates were characterised under similar conditions to such experiments where biomarker hydrocarbons undergo minimal rearrangement. Compounds identified by gas chromatography–mass spectrometry included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines and benzoquinolines.Indoles are present in all hydropyrolysates, suggesting a common origin. A potential source of indoles is represented by tryptophan which was shown to degrade through a series of alkylated intermediates to indole. Carbazole, quinoline and benzoquinoline were also found in the hydropyrolysates of algae, bacteria and archaea. The presence of these petroleum-related nitrogen compounds in hydropyrolysates generated from biomass suggests an early origin for petroleum nitrogen compounds. A potential source of naturally occurring nitrogen compounds such as that in the alkaloids has yet to be realised.Benzocarbazoles were absent from hydropyrolysates of algae, bacteria and archeae, but present in those from recent sediments, suggesting their presence may be related to processes occurring during early diagenesis at, or immediately below, the sediment–water interface. In sediments from Lake Pollen, changes in the benzocarbazole ratio [a]/([a] + [c]) ratio coincides with the interval described as a transition from fjord to lake environment, suggesting that benzocarbazoles are sensitive to changes in depositional environment and may have potential to act as a marker for environmental conditions.     

Beyond Modelling: Linking Models with GIS for Flood Risk Management

Spatially explicit hydrodynamic flood models can play animportant role in natural hazard risk reduction. A key element of these models that make them suitable for riskreduction is the ability to provide time-series inundation information about the onset, duration and passingof a hazard event. Such information can be critical for landuse planning, for mapping evacuation egress routes,and for locating suitable emergency shelters to name only a few risk treatments. This research contends that abarrier to effective risk reduction is providing disaster managers with access to model results in a structured andflexible framework that allows consequences of different hazard scenarios to be assessed and mapped. Toaddress these limitations, a framework has been developed that links a commercial relational databasemanagement system with a GIS-based decision support system. The framework utilises industry standard dataexchange protocols and results in efficient time-series hazard data management. A case study based in Cairns,in far-north coastal Australia is presented to illustrate how the system has been developed. Results show that theframework reduces data volumes significantly, while making pre-run modelled inundation results rapidly accessibleto disaster managers. Of note is the ability of the framework to present results in terms of risk to buildings,roads and other spatial features in urban regions, and to provide answers to relatively complex risk questions.     

Atmospheric Disturbances that Generate Intermittent Turbulence in Nocturnal Boundary Layers

Using the unprecedented observational facilities deployed duringthe 1999 Cooperative Atmosphere-Surface Exchange Study (CASES-99),we found three distinct turbulent events on the night of 18October 1999. These events resulted from a density current,solitary wave, and internal gravity wave, respectively. Our studyfocuses on the turbulence intermittency generated by the solitarywave and internal gravity wave, and intermittent turbulenceepisodes associated with pressure change and wind direction shiftsadjacent to the ground. Both the solitary and internal gravitywaves propagated horizontally and downward. During the passage ofboth the solitary and internal gravity waves, local thermal andshear instabilities were generated as cold air was pushed abovewarm air and wind gusts reached to the ground. These thermal andshear instabilities triggered turbulent mixing events. Inaddition, strong vertical acceleration associated with thesolitary wave led to large non-hydrostatic pressure perturbationsthat were positively correlated with temperature. The directionaldifference between the propagation of the internal gravity waveand the ambient flow led to lateral rolls. These episodic studiesdemonstrate that non-local disturbances are responsible for localthermal and shear instabilities, leading to intermittentturbulence in nocturnal boundary layers. The origin of thesenon-local disturbances needs to be understood to improve mesoscalenumerical model performance.     

Trace elements in streambed sediments of small subtropical streams on O‘ahu, Hawai‘i: Results from the USGS NAWQA program

Data are presented for trace element concentrations determined in the <63 μm fraction of streambed sediment samples collected at 24 sites on the island of O‘ahu, Hawai‘i. Sampling sites were classified as urban, agricultural, mixed (urban/agricultural), or forested based on their dominant land use, although the mixed land use at selected sampling sites consisted of either urban and agricultural or forested and agricultural land uses. Forest dominated sites were used as reference sites for calculating enrichment factors.Trace element concentrations were compared to concentrations from studies conducted in the conterminous United States using identical methods and to aquatic-life guidelines provided by the Canadian Council of Ministers of the Environment. A variety of elements including Pb, Cr, Cu and Zn exceeded the aquatic-life guidelines in selected samples. All of the Cr and Zn values and 16 of 24 Cu values exceeded their respective guidelines. The potential toxicity of elements exceeding guidelines, however, should be considered in the context of strong enrichments of selected trace elements attributable to source rocks in Hawai‘i, as well as in the context of the abundance of fine-grained sediment in the streambed of O‘ahu streams.Statistical methods including cluster analysis, Kruskal–Wallis non-parametric test, correlation analysis, and principal component analysis (PCA) were used to evaluate differences and elucidate relationships between trace elements and sites. Overall, trace element distributions and abundances can be correlated to three principal sources of elements. These include basaltic rocks of the volcanic edifice (Fe, Al, Ni, Co, Cr, V and Cu), carbonate/seawater derived elements (Mg, Ca, Na and Sr), and elements enriched owing to anthropogenic activity (P, Sn, Cd, Sn, Ba and Pb). Anthropogenic enrichment gradients were observed for Ba, Cd, Pb, Sn and Zn in the four streams in which sediments were collected upstream and downstream.The findings of this study are generally similar to but differ slightly from previous work on sediments and suspended particulate matter in streams, from two urban watersheds of O‘ahu, Hawai‘i. Inter-element associations in the latter were often stronger and indicated a mixture of anthropogenic, agricultural and basaltic sources of trace elements. Some elements fell into different statistical categories in the two studies, owing in part to differences in study design and the hydrogeological constraints on the respective study areas.     

Evidence from kimberlitic zircon for a decreasing mantle Th/U since the Archean

A decoupling in MORB of measured Th/U (κ = 2.5) from that calculated by Pb isotopes (κ = 3.8) for the depleted asthenosphere is well established, and has been referred to as the second Pb paradox (Kramers, J.D., and Tolstikhin, I.N., 1997. Two terrestrial lead isotope paradoxes, forward transport modelling, core formation and the history of the continental crust. Chem. Geol., 139, 75–110.) or the kappa conundrum (Elliott, T., Zindler, A., and Bourdon, B., 1999. Exploring the kappa conundrum: the role of recycling in the lead isotope evolution of the mantle. Earth Planet. Sci. Lett., 169, 129–145.). More controversial has been the cause and timing of this phenomenon, although a higher return flux of U⁶⁺ relative to Th⁴⁺ and(or) the recycling of crustal Pb into the mantle have become the preferred explanations of most workers. Such a combined mechanism effectively operating over the past 2.5 Ga was modelled in plumbotectonics (Zartman, R.E., and Haines, S., 1988. The plumbotectonics model for Pb isotopic systematics among major terrestrial reservoirs—a case for bi–directional transport. Geochim. Cosmochim. Acta, 52, 1327–1339. 709.33.), and found to be quantitatively feasible.A large TIMS, SIMS and LA-ICPMS database of Th and U concentrations for kimberlite-hosted zircon, particularly from Cr-poor megacrystic suites, now exists (Kinny et al., 1989, Berryman et al., 1999, Griffin et al., 2000 and Spetsius et al., 2002; Appendix A and Appendix B, this work). Six suites comprising 10 or more zircon grains with ages between 90 and 2550 Ma reveal consistent patterns when plotted on Th/U vs. U diagrams. We interpret these patterns as resulting from fractional crystallization of a melt with kimberlite affinity presumably derived from the asthenosphere, permitting the extrapolation to an initial Th/U at the time zircon crystallization began. A two-fold decrease is seen in this ratio over the past 2.5 Ga, suggesting that during this time a similar change has occurred in the parent silicate melt. Estimates of Th and U distribution coefficients between zircon and coexisting melt permit calculation of Th/U in the melt, which, for these highly incompatible elements, presumably is the same as for its mantle source rock. Kimberlitic zircon may thus indeed give evidence of a reduction in κ, tentatively calculated as from 4 to 2, since the Archean for the depleted asthenosphere.     

Evolution of Palaeoproterozoic mafic intrusions located within the thermal aureole of the Sudbury Igneous Complex, Canada: Isotopic, geochronological and geochemical evidence

Impact cratering and their resultant geological phenomena are recognised as significant factors in the lithological and biologic evolution of the earth. Age-dating of impact events is critical in correlating cause and effects for these catastrophic processes. The Falconbridge and Drury Township (Twp) intrusions were emplaced at the contact between Neoarchaean basement and Palaeoproterozoic volcanosedimentary rocks, and also lie at the southeast and southwest edges of the Sudbury Igneous Complex (SIC), within its thermal contact aureole. The Falconbridge Twp intrusion is dated at 2441 ± 3 Ma by U-Pb zircon, with evidence of Archaean inheritance from its host granitoids. Granitoids from the southernmost Abitibi Subprovince are dated here between 2670 ± 11 Ma for an undeformed Algoman granite, and 2696 ± 18 Ma for a foliated granitoid, consistent with existing data from the Abitibi Greenstone Belt and from the Wawa Subprovince. Major and trace element geochemical evidence, common-Pb isotopic compositions, and εNd2440 values between 0 and −1 are all consistent with a Palaeoproterozoic origin for the Falconbridge Twp intrusion, and support inclusion in the East Bull Lake-type suite of leucogabbroic plutons and sills.In contrast, the Drury Twp intrusion gives a U-Pb zircon age of 1859 ± 13 Ma, coincident with the date of SIC-emplacement. While the major and trace element compositions are comparable to the Falconbridge data, the Drury displays significant heterogeneity in εNd2440, with values ranging from +3.7 to −0.1, and contains more radiogenic Pb isotopic compositions. Field, geochemical and isotopic evidence clearly distinguishes this intrusion from constituents of the SIC itself, and indicates that the Drury too is a Palaeoproterozoic intrusion. This requires that apparently unshocked, undeformed magmatic-looking zircon has been grown or reset in a postmagmatic setting. This has significant implications for the identification of mantle-derived magmas and crustal remelts associated with large impact craters. A resetting mechanism involving aggressive hydrothermal alteration of zircon facilitated by halogen-complexing is proposed, inducing rapid, postshock lead loss and subsequent annealing.     

Oxygen isotope fractionation during synthesis of CaMg-carbonate and implications for sedimentary dolomite formation

Hydrous CaMg-carbonate was synthesized at temperatures of 40°, 60° and 80°C in the laboratory. This material has very similar mineralogical characteristics to natural disordered dolomite from the Coorong region in South Australia. Besides the dolomite variable amounts of amorphous carbonate are present in all samples. The oxygen isotope compositions of synthesized bulk carbonate samples (e.g., amorphous carbonate plus dolomite) plot significantly lower than the Northrop and Clayton (1966) dolomite-water equilibrium. Fractionated degassing of the samples, however, revealed relatively low oxygen isotope values for fast-reacting (using 100% H₃PO₄) amorphous carbonate. In contrast, slow-reacting dolomite has more positive oxygen isotope values, and calculated carbonate-water oxygen isotope fractionation values are close to strongest known dolomite-water oxygen isotope fractionation published earlier on. Variations of reaction/stabilization temperatures during synthesis gave evidence for dolomite formation from hypersaline solutions by a dissolution/reprecipitation process. It is likely that amorphous carbonate has been a problem in defining the dolomite-water fractionation in the past. Moreover, dolomite-associated amorphous carbonate contents probably led to incorrect speculations about lower oxygen isotope fractionation in a so-called protodolomite-water system.