Nickeliferous sulfides in xenoliths,olivine megacrysts and basaltic glass

The composition of olivine and nickeliferous sulfide inclusions from a selection of mafic and ultramafre rocks, xenoliths and megacrysts, including picritic basalts from Kilauea Volcano, Hawaii, kimberlite from Fayette County, Pennsylvania, and megacrysts from Mount Shasta, California are compared with the mean experimental value of the distribution coefficient for Ni/Fe exchange (K_D3=32). Only nine of the forty five olivipe/bulk-sulfide pairs investigated have compositions consistent with equilibration at high temperature, yielding calculated K_D3 values in the range 22 to 41. The remaining pairs have calculated K_D3 values which range from 0 to 19. Bulk-sulfides in disequilibrated assem-blages are consistently depleted in nickel and within both indivudual associations and individual petrographic sections they exhibit a wide variation in NiS content. The bulk copper contents of olivine-and groundmass-hosted sulfides from Kilauea Volcano range from 0.5 to 43 at%, and samples from the Kilauea Iki lava lake are more Fe-and Cu-rich and generally have lower K_D3 values than those from the eruption itself. As with magmatic Ni–Cu sulfide deposits, most nickeliferous sulfide inclusions in mantle-related rocks and xenoliths and in volcanic rocks do not have pristine early-magmatic bulk compositions, and it would seem to be premature to attribute these sulfides solely to either a mantle or an early-magnatic origin.     

Dynamical formulation of Broecker''s model for marine cycles of biologically incorporated elements

Broecker presented a steady-state, two-box model which emphasizes the role of kinetic factors in determining the chemical composition of sea water. Unlike thermodynamic models, Broecker's model suggests that sizable temporal variation in the composition of sea water and rates of sedimentation may have taken place in the past 100 million years. To describe the evolution of the ocean's chemical system and interpret variations observed in the sedimentary record, we have formulated a dynamical model. Mass-balance consideration leads to a set of coupled nonlinear differential equations. The equations are linearized and solved for step function changes in the rate of river input and in the rate of vertical mixing. This simple model of the ocean's chemical system is shown to be stable against oscillations. Using data for the modern ocean, the response times for P, C, Si, Ca, and Ba are calculated to be of the order of 10⁴ to 10⁶ yr for changes in river and other inputs and of the order 10¹ to 10² yr for a change in the rate of vertical mixing. Analog-simulation techniques, discussed for the situation of the two-box model, provide a powerful tool for treating nonlinearities and systems with more than two components. In the final section, consequences of the dynamical formulation are compared with parameters appearing in Broecker's steady-state formulation.     

Confocal laser scanning microscopy and Raman imagery of ancient microscopic fossils

Among all problems confronting the study of ancient permineralized (petrified) microscopic fossils, two stand out, the need for (1) accurate documentation of their three-dimensional morphology, and (2) direct analysis of their chemical composition and that of their surrounding mineral matrices. To address these problems we demonstrate the use of two techniques that we have recently introduced to Precambrian paleobiology: confocal laser scanning microscopy and Raman imagery. These techniques, both of which are non-intrusive and non-destructive, can provide data by which to characterize, in situ and at micron-scale resolution, the cellular and organismal morphology of thin section-embedded organic-walled fossils. In addition, Raman imagery provides direct analyses of the molecular–structural composition of the kerogenous components of such fossils and of their surrounding matrices, and a means to assess quantitatively the geochemical maturity of the preserved organics. Use of these techniques for studies of ancient microscopic fossils can provide information in three dimensions at high spatial resolution about their morphology and cellular anatomy, taphonomy and fidelity of preservation, composition and mode of preservation, and their biogenicity and syngenetic origin with the rocks in which they occur.     

Probabilistic seismic hazard assessment for some parts of the Indo-Gangetic plains,India

Natural Hazards - Indo-Gangetic plains are seismically most vulnerable due to the proximity of adjacent great Himalayan earthquakes and thick alluvium deposits of the Ganga River system. As the...     

Relations between hydrology and velocity of a continuously moving landslide—evidence of pore-pressure feedback regulating landslide motion?

We measured displacement, pore-water pressure, and climatic conditions for 3 years at the continuously moving Slumgullion landslide in Colorado, USA. The landslide accelerated when pore-water pressure increased within the landslide body, but this occurred as pore-water pressure decreased along the landslide margin. The decrease probably occurred in response to shear-induced soil dilation at rates greater than pore-pressure diffusion and likely increased resistance to shear displacement and resulted in landslide deceleration. This dilative strengthening has been experimentally observed and explained theoretically, but not previously identified during field studies. Although landslide displacement should have exceeded that required to achieve critical-state density of shear boundaries, observed relocation of these boundaries indicates that shearing is episodic at fixed locations, so it permits renewed dilative strengthening when “fresh” soil is sheared. Thus, dilatant strengthening may be a considerable mechanism controlling landslide velocity, even for landslides that have continuously moved great distances.     

Electronic environments in carrollite, CuCo2S4, determined by soft X-ray photoelectron and absorption spectroscopy

Fracture surfaces of a natural carrollite specimen have been characterised by synchrotron and conventional X-ray photoelectron spectroscopy and near-edge X-ray absorption spectroscopy. For the synchrotron X-ray measurements, the mineral surfaces were prepared under clean ultra high vacuum and were unoxidised. The characterisation was undertaken primarily to establish unequivocally the oxidation state of the Cu in the mineral, but also to obtain information on the electronic environments of the Co and S, and on the surface species. Experimental and simulated Cu L_2,3-edge absorption spectra confirmed an oxidation state of Cu^I, while Co 2p photoelectron and Co L_2,3 absorption spectra were largely consistent with the Co^III established previously by nuclear magnetic resonance spectroscopy. S 2p photoelectron spectra provided no evidence for S to be present in the bulk in more than one state, and were consistent with an oxidation state slightly less negative than S^-II. Therefore it was concluded that carrollite can be best represented by Cu^ICo^III₂(S₄)^-VII. The Cu^I oxidation state is in agreement with that expected for Cu tetrahedrally coordinated by S, but is in disagreement with the Cu^II deduced previously from some magnetic, magnetic resonance and Cu L-edge X-ray absorption spectroscopic measurements. A significant concentration of S species with core electron binding energies both lower and higher than the bulk value were formed at fracture surfaces, and these entities were assigned to monomeric and oligomeric surface S species. The density of Cu d states calculated for carrollite differed from that previously reported but was consistent with the observed Cu L₃ X-ray absorption spectrum. The initial oxidation of carrollite in air under ambient conditions was confirmed to be congruent, unlike the incongruent reaction undergone by a number of non-thiospinel sulfide minerals.     

Observed Spatial and Temporal Distributions of CVOCs at Colorado and New York Vapor Intrusion Sites

The vapor intrusion impacts associated with the presence of chlorinated volatile organic contaminant plumes in the ground water beneath residential areas in Colorado and New York have been the subject of extensive site investigations and structure sampling efforts. Large data sets of ground water and indoor air monitoring data collected over a decade-long monitoring program at the Redfield, Colorado, site and monthly ground water and structure monitoring data collected over a 19-month period from structures in New York State are analyzed to illustrate the temporal and spatial distributions in the concentration of volatile organic compounds that one may encounter when evaluating the potential for exposures due to vapor intrusion. The analysis of these data demonstrates that although the areal extent of structures impacted by vapor intrusion mirrors the areal extent of chlorinated volatile organic compounds in the ground water, not all structures above the plume will be impacted. It also highlights the fact that measured concentrations of volatile organic compounds in the indoor air and subslab vapor can vary considerably from month to month and season to season. Sampling results from any one location at any given point in time cannot be expected to represent the range of conditions that may exist at neighboring locations or at other times. Recognition of this variability is important when designing sampling plans and risk management programs to address the vapor intrusion pathway.     

Physical,chemical, and biological conditions associated with the early stages of the Lake Michigan vernal thermal front

An investigation of the thermal front in southeastern Lake Michigan during April 1988 revealed a dynamic physical, chemical, and biological environment. The front was observed approximately 4 km from the coast as a distinct gradient separating cold open-lake waters from warmer nearshore waters. Surface isotherms near the front were generally parallel to one another but skewed with respect to shore. Comparison between April 22 and 29 showed that the surface isothern pattern was modulated by wind stress. The pattern from April 29 showed signs of flow instabilities with horizontal scales of 1 km to 5 km. Surface drifter trajectories provided estimates of horizontal convergence at the fron which varied from 7×10^?6 s^?1 to 20×10^?6 s^?1. Inferred rates of downwelling, which ranged from 9.5 m d^?1 to 20.7 m d^?1, were sufficient to move a water parcel from the surface to the bottom in 2 to 6 d at the front. Convergent circulation was observed on both sampling dates despite contrasts in wind stress. Concentrations of chloride, soluble silica, and chlorophyll, which were always higher inshore, were 5% to 82% larger than offshore mean values. The aquatic environment just inshore of the thermal front was characterized by chlorphyll concentrations which exceeded 5.0 μg 1^?1 while concentrations offshore were between 1.0 μg 1^?1 and 2.0 μg 1^?1. A relatively uniform vertical structure in chlorophyll concentrations in the frontal zone was consistent with the observed convergence and inferred downwelling near the front.