Structure proof and significance of stereoisomeric 28,30-bisnorhopanes in petroleum and petroleum source rocks

Two C₂₈H₄₈-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring $\text{D}\text{E}$cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.     

Recent progress on combining geomorphological and geochronological data with ice sheet modelling,demonstrated using the last British–Irish Ice Sheet

Palaeo-ice sheets are important analogues for understanding contemporary ice sheets, offering a record of ice sheet behaviour that spans millennia. There are two main approaches to reconstructing palaeo-ice sheets. Empirical reconstructions use the available glacial geological and chronological evidence to estimate ice sheet extent and dynamics but lack direct consideration of ice physics. In contrast, numerically modelled simulations implement ice physics, but often lack direct quantitative comparison with empirical evidence. Despite being long identified as a fruitful scientific endeavour, few ice sheet reconstructions attempt to reconcile the empirical and model-based approaches. To achieve this goal, model-data comparison procedures are required. Here, we compare three numerically modelled simulations of the former British–Irish Ice Sheet with the following lines of evidence: (a) position and shape of former margin positions, recorded by moraines; (b) former ice-flow direction and flow-switching, recorded by flowsets of subglacial bedforms; and (c) the timing of ice-free conditions, recorded by geochronological data. These model–data comparisons provide a useful framework for quantifying the degree of fit between numerical model simulations and empirical constraints. Such tools are vital for reconciling numerical modelling and empirical evidence, the combination of which will lead to more robust palaeo-ice sheet reconstructions with greater explicative and ultimately predictive power.     

A constitutive model for municipal solid waste considering mechanical creep and biodegradation-induced compression

Acta Geotechnica - A constitutive model is developed to describe the stress–strain–time behavior for decomposing municipal solid waste (MSW) within a critical state soil mechanics...     

Quantitative 3D imaging of partially saturated granular materials under uniaxial compression

Acta Geotechnica - Gauging the mechanical effect of partial saturation in granular materials is experimentally challenging due to the very low suctions resulting from large pores. To this end, a...     

A groundwater salinity hotspot and its connection to an intermittent stream identified by environmental tracers (Mt Lofty Ranges,South Australia)

High and variable levels of salinity were investigated in an intermittent stream in a high-rainfall area (～800 mm/year) of the Mt. Lofty Ranges of South Australia. The groundwater system was found to have a local, upslope saline lens, referred to here as a groundwater salinity ‘hotspot’. Environmental tracer analyses (δ¹⁸O, δ²H, ^87/86Sr, and major elements) of water from the intermittent stream, a nearby permanent stream, shallow and deep groundwater, and soil-water/runoff demonstrate seasonal groundwater input of very saline composition into the intermittent stream. This input results in large salinity increases of the stream water because the winter wet-season stream flow decreases during spring in this Mediterranean climate. Furthermore, strontium and water isotope analyses demonstrate: (1) the upslope-saline-groundwater zone (hotspot) mixes with the dominant groundwater system, (2) the intermittent-stream water is a mixture of soil-water/runoff and the upslope saline groundwater, and (3) the upslope-saline-groundwater zone results from the flushing of unsaturated-zone salts from the thick clayey regolith and soil which overlie the metamorphosed shale bedrock. The preferred theory on the origin of the upslope-saline-groundwater hotspot is land clearing of native deep-rooted woodland, followed by flushing of accumulated salts from the unsaturated zone due to increased recharge. This cause of elevated groundwater and surface-water salinity, if correct, could be widespread in Mt. Lofty Ranges areas, as well as other climatically and geologically similar areas with comparable hydrogeologic conditions.     

A kinetic model of metamorphism: an application to siliceous dolomites

We use a kinetic model of a metamorphic system to study the effect of competing rates of reaction, fluid injection, and heating on the evolution of the reaction pathway in temperature/composition space at constant pressure. We show that for rocks in contact with mixed volatile (e.g., CO₂-H₂O) fluids the reaction path may be quite different from what is expected from equilibrium-based petrologic models. Equilibrium-based models, used to understand the development of rock systems undergoing mineral reactions during a metamorphic event, rely on the Gibbs phase rule and only consider stable phases. For constant pressure, the temperature-composition paths follow univariant curves and significant reactions may occur at invariant points. By contrast, the more general kinetic treatment is not constrained by equilibrium, although with the proper competing rates equilibrium is a possible endmember of the kinetic approach. The deviation from equilibrium depends on the competing rates of reaction, heating, and fluid injection. A key element required by the kinetic approach is the inclusion of metastable reactions in the formulation, whereas such reactions are irrelevant for equilibrium-based models. Metastable reactions are often involved in a complex interplay with common prograde stable metamorphic reactions. We present model results for the well-studied CaO-MgO-SiO₂-CO₂-H₂O (CMS) system to show how the system evolves under kinetic control. Our simulations and discussion focus on the behavior of the CMS system under a number of closed and open system conditions. Special attention is paid to closed system behavior in the vicinity of the (first) isobaric invariant point (with Dol, Qtz, Tlc, Cal, and Tr). Also, for open systems with massive fluid infiltration we consider heating rates varying from contact to regional metamorphic conditions. For some geologically reasonable rates of reactions, heating, and fluid injection, our results demonstrate that equilibrium conditions may be significantly overstepped in metamorphic systems. We used overall mineral reactions in this model with rates based on experimental results. Future models could rely on more fundamental dissolution and precipitation reactions. Such an extension would require additional kinetic rate data, as well as mineral solubilities in mixed volatile fluids.Editorial responsibility: J. Hoefs     

Melt density and the average composition of basalt

Densities of residual liquids produced by low pressure fractionation of olivine-rich melts pass through a minimum when pyroxene and plagioclase joint the crystallization sequence. The observation that erupted basalt compositions cluster around the degree of fractionation from picritic liquids corresponding to the density minimum in the liquid line of descent may thus suggest that the earth's crust imposes a density filter on the liquids that pass through it, favoring the eruption of the light liquids at the density minimum over the eruption of denser more fractionated and less fractionated liquids.     

Orthophosphate and biotite chemistry from orthopyroxene-bearing migmatites from California and South India: The role of a fluid-phase in the evolution of granulite-facies migmatites

Migmatites from Cone Peak, California, USA and the Satnur-Sangam road, Southern Karnataka, India contain coarser grained orthopyroxene-bearing leucosomes with subordinate biotite in finer grained hornblende-biotite-pyroxene-bearing hosts. At both localities the leucosomes are enriched in quartz and feldspar and have a higher ratio of pyroxene to hornblende + biotite compared to the host rocks. Biotite grains in leucosomes along the Satnur-Sangam road are concentrated at the margins of orthopyroxene grains and have lower abundances of Ti, Fe, and Cl and a higher abundance of F than biotite grains from the host rock. Fluorapatite grains in all rocks from both localities contain monazite inclusions similar to those produced experimentally by metasomatically induced dissolution and reprecipitation. Some fluorapatite grains at both localities are partially rimmed by allanite. The only compositional differences found between fluorapatite grains in the leucosomes and host rocks were higher concentrations of Cl in grains in leucosomes from Cone Peak. The mineralogies of the rocks suggest that the leucosomes formed by dehydration melting reactions that consumed feldspar, quartz, hornblende, and biotite and produced orthopyroxene. Allanite rims at the margins of fluorapatite grains may have formed by the later retrogression of monazite rims formed by incongruent dissolution of fluorapatite in the melt. Biotite grains at the margins of orthopyroxene crystals in the leucosomes from the Satnur-Sangam road apparently formed by retrogression of orthopyroxene upon the solidification of the anatectic melt. A similar high-grade retrogression did not affect orthopyroxene crystals at Cone Peak, indicating that H₂O was removed from the crystallizing leucosomes probably in a low H₂O activity fluid. Compositional differences between the paleosome and neosomes at Cone Peak are best explained by metasomatic interaction with concentrated brines while elevated Cl concentrations in fluorapatites in the leucosome suggest interaction with a Cl-bearing fluid. Brines may have been responsible for an exchange of elements between the host rock along the Satnur-Sangam road and zones of melt generation now marked by leucosomes, but fluid flow appears to have been less vigorous than at Cone Peak.     

A three dimensional perspective on the evolution of Archaean crust: LITHOPROBE seismic reflection images in the southwestern Superior province

15011993

Abstract

In 1990–1991 the LITHOPROBE project completed 450 km of seismic reflection profiles across the late Archaean crust of the southwestern Superior province. The results define a broad three-fold division of crust: upper crust in the Abitibi greenstone belt is non-reflective and is a 6–8 km veneer of volcanic and plutonic supracrustal rocks, whereas, in the sediment-gneiss dominated Pontiac subprovince, upper crust comprises shallow northwest-dipping turbidite sequences; mid-crust, in both the Abitibi and the Pontiac subprovinces, is interpreted as imbricate sequences of metasedimentary and metaplutonic rocks; lower crust in both subprovinces has a horizontal layer parallel strycture which may represent interleaved mafic-intermediate gneisses. The seismic signature of the northern Abitibi greenstone belt may be represented in an exposed 25 km crustal section in the Kapuskasing stuctural zone.

Preliminary tectonic models based on the seismic data are consistent with a plate-tectonic scenario involving oblique subduction and imbrication of sedimentary, plutonic and volcanic sequences. The northern Abitibi supracrustal sequences either represent an allochthon, or overlie an allochthonous underthrust metasedimentary and plutonic sequence which may be equivalent to a metasedimentary subprovince such as the Pontiac or Quetico.

Seismic velocities have yet to be defined. However, crustal thicknesses are relatively constant at 35–40 km. The thinnest crust is adjacent to the Grenville Front where Moho is very well defined.     

Neighborhood covenants and restrictions: an examination of fit

Covenants and restrictions (C&Rs) have increased in popularity in recent decades, being commonly applied in new residential developments. Despite the fact that developers are more commonly writing C&Rs for their developments, little research has investigated how well C&Rs actually fit the preferences of residents. Recognizing this gap in the literature, this paper examines the fit of neighborhood C&Rs with resident preferences in Porter County, Indiana, a growing suburban/exurban place in the Chicago Metropolitan Statistical Area. The researcher conducted in-depth interviews with 51 residents to ascertain how well C&Rs fit resident preferences. The majority of interviewees stated that C&Rs match resident preferences because they believed that C&Rs promoted subdivision tidiness and worked to support property values. The minority view was that C&Rs do not fit because they are too strict and residents do not obey C&Rs. Interviewees who perceived a fit were more likely to have a lower level of engagement with C&Rs and were more likely to live in developments with no C&R enforcement attempts by the homeowners’ association (HOA). The results suggest the particular content of C&Rs does not seem to fit resident preference; rather the fact that C&Rs are not enforced fits resident preference. Seemingly, residents are content being unaware of the C&Rs, then they do not know if someone is breaking the rules or not. This may imply that residents would not want to have C&Rs in the first place.