Polarization in spectral lines

The general formalism, presented in a previous paper of this series (Landi Degl'Innocenti, 1983a), is particularized to deduce the radiative transfer equations for polarized radiation and the statistical equilibrium equations for a multi-level atom in the zero-magnetic field, collisionless regime. The formulae are developed both in the standard representation and in the representation of the statistical tensors. For resonance scattering in a two-level atom, in the limiting case of complete depolarization of the ground level, we recover the classical results for Rayleigh scattering and we derive the expression of the phase matrix in terms of ordinary rotation matrices. The law of scattering is then generalized to take properly into account the influence of the anisotropy of the radiation field on the atomic polarization of the ground level (depopulation pumping).     

Experimental investigation of the combustive sound source

In this paper, we describe a unique low frequency underwater sound source called the combustive sound source (CSS). In this device, a combustible gas mixture is captured in a combustion chamber and ignited with a spark. The ensuing combustion produces expanding gases which in turn produce high intensity, low frequency acoustic pulses. With high-speed motion pictures of the CSS event, we relate the motion of the bubble to the acoustic waveform. We also compare the measured first bubble period in the CSS pressure signature with the predictions of the Rayleigh-Willis equation, including the dependence of the radiated acoustic waveform on the volume and depth of the bubble. Measurements of the first bubble period agree with Rayleigh-Willis theory in trend, but not in absolute value. In addition, we discuss the variation of the acoustic output with the fuel/oxygen mixture. Finally, several other factors that affect the acoustic output of CSS are discussed. These include the shape of the CSS combustion chamber, the type of oxidizer and fuel, and the ignition source     

Contrasting geochemical signatures on land from the Middle and Late Permian extinction events

The end of the Palaeozoic is marked by two mass‐extinction events during the Middle Permian (Capitanian) and the Late Permian (Changhsingian). Given similarities between the two events in geochemical signatures, such as large magnitude negative δ¹³C anomalies, sedimentological signatures such as claystone breccias, and the approximate contemporaneous emplacement of large igneous provinces, many authors have sought a common causal mechanism. Here, a new high‐resolution continental record of the Capitanian event from Portal Mountain, Antarctica, is compared with previously published Changhsingian records of geochemical signatures of weathering intensity and palaeoclimatic change. Geochemical means of discriminating sedimentary provenance (Ti/Al, U/Th and La/Ce ratios) all indicate a common provenance for the Portal Mountain sediments and associated palaeosols, so changes spanning the Capitanian extinction represent changes in weathering intensity rather than sediment source. Proxies for weathering intensity chemical index of alteration, ?W and rare earth element accumulation all decline across the Capitanian extinction event at Portal Mountain, which is in contrast to the increased weathering recorded globally at the Late Permian extinction. Furthermore, palaeoclimatic proxies are consistent with unchanging or cooler climatic conditions throughout the Capitanian event, which contrasts with Changhsingian records that all indicate a significant syn‐extinction and post‐extinction series of greenhouse warming events. Although both the Capitanian and Changhsingian event records indicate significant redox shifts, palaeosol geochemistry of the Changhsingian event indicates more reducing conditions, whereas the new Capitanian record of reduced trace metal abundances (Cr, Cu, Ni and Ce) indicates more oxidizing conditions. Taken together, the differences in weathering intensity, redox and the lack of evidence for significant climatic change in the new record suggest that the Capitanian mass extinction was not triggered by dyke injection of coal‐beds, as in the Changhsingian extinction, and may instead have been triggered directly by the Emeishan large igneous province or by the interaction of Emeishan basalts with platform carbonates.     

The scope for generating bio-oils with relatively low oxygen contents via hydropyrolysis

The primary oils obtained in high yields from fast (fluidised-bed) pyrolysis of biomass generally have high oxygen contents (ca. 40% w/w). The scope for using pyrolysis under hydrogen pressure (hydropyrolysis), to give oils with much lower oxygen contents compared to normal pyrolysis has been investigated. Fixed-bed hydropyrolysis tests have been conducted on cellulose, sugar cane bagasse and eucalyptus wood using hydrogen pressures up to 10 MPa, with heating rates of 5 and 300°C min⁻¹. A colloidal FeS catalyst was used in some tests (Fe loading of 5%, w/w) to increase overall conversions. Further, the attractive option of using a two-stage reactor in which the primary oil vapors are passed though a bed of hydrotreating catalyst is also described. Raising the hydrogen pressure from atmospheric to 10 MPa reduced the oxygen content of the primary oil by over 10% to below 20% w/w. The addition of a dispersed iron sulphide catalyst gave conversions close to 100% for all three biomass samples investigated at 10 MPa under conditions in the fixed-bed reactor where significant diffusional resistances existed and reduced the oxygen content of the bio-oil by a further 10%. Although NMR indicated that the oils became increasingly aromatic as more oxygen was removed, the increase in hydrogen pressure decreased the extent of overall aromatisation that occurs primarily due to the lower char yields obtained. In two-stage tests for cellulose, using a commercial sulphided Ni/Mo γ-Al₂O₃ catalyst at 400°C, increasing the hydrogen pressure from 2.5 to 10 MPa decreased the oxygen content of the oil by over 20% to 10% w/w. The H/C ratios were higher and O/C ratios smaller for the two-stage bio-oils compared to their single stage counterparts. However, the differences in the O/C ratios between the single and two-stage bio-oils increase with pressure.     

Source(s) and cycling of the nonhydrolyzable organic fraction of oceanic particles

A major fraction of particulate organic carbon (POC) in the deep ocean remains molecularly uncharacterized. In an effort to determine the chemical characteristics and source(s) of sinking POC, we studied a nonhydrolyzable fraction of sinking POC using ¹³C NMR (nuclear magnetic resonance) spectroscopy and analytical pyrolysis. ¹³C NMR spectra and products from analytical pyrolysis of the nonhydrolyzable fraction exhibit a strongly aliphatic character that is distinct from that of bulk POC. The aliphatic nature of this fraction is consistent with its low stable carbon isotope values. We hypothesize that the nonhydrolyzable fraction derives to a significant extent from a refractory component of organisms that selectively accumulates, resulting in its manifestation as a major part of POC sinking to the deep ocean and in underlying sediments.     

Polycyclic aromatic hydrocarbons in commercial fish and lobsters from the coastal waters of Madagascar following an oil spill in August 2009

Concentrations of polycyclic aromatic hydrocarbons were determined in species of commercial fish and lobsters following an oil-spill just off the protected Madagascan coastline. Samples were collected along the coastline within and outside the affected area. Summed PAH concentrations ranged from 1.9 μg kg⁻¹ to 63 μg kg⁻¹ wet weight, but with no higher molecular weight PAHs (>202 Da) being detected. All concentrations of benzo[a]pyrene, benz[a]anthracene and dibenz[a,h]anthracene were <0.1 μg kg⁻¹ wet weight, well within the EU and UK set limits for the protection of human health. Additionally, samples were calculated as the benzo[a]pyrene toxic equivalency quotient (TEQ) and found to be well below the level of concern in relation to health of human consumers. Evaluation of the biota PAH data indicated the origin of PAH was predominantly petrogenic with >80% arising from oil sources. Profile studies indicate a low-level multisource petrogenic contamination probably representing a pre-spill background for the area.     

Couplage des équations de transfert de masse et des lois d''interactions solution-solide par l''utilisation des lanthanides comme traceurs — Approche expérimentale

In underground flow tracing studies, the estimation of the nature and the importance of interactions undergone by the substance used very often constitutes an obstacle to good modeling of mass-transfer processes in solution.

We propose a method to quantify these phenomena by the use of lanthanides as tracers.

For this study, we set up an analytical methodology adapted to routine measurements. The quality of five lanthanides as indicators has been examined. We have demonstrated the formation, by substitution, of a carbonate complex which is extremely stable in the natural environment. The field experiments carried out demonstrated the efficiency of those tracers and confirmed their great stability.

Tracer recovery graphs show that, in accord with our hypothesis, convection and dispersion are identical for all the lanthanide elements. Moreover, we have established a direct relation between their fixing rate on earth materials and the value of their stability constants.

Thus, we demonstrate the possibility of correlative multitracing, with known and quantifiable interelement relations.

Résumé

Dans les études de circulations souterraines par traceur, l'estimation de la nature et de l'importance des interactions subies par la substance utilisée constitue, bien souvent, un obstacle à une bonne modélisation des processus de transfert de masse en solution.

Nous proposons une méthode de quantification de ces phénomènes par l'utilisation des lanthanides comme traceurs.

Pour cette étude, nous avons mis au point une méthodologie analytique adaptée aux mesures de routine. Les qualités, en tant qu'indicateurs, de cinq lanthanides ont été examinées. Nous avons démontré la formation, par substitution, d'un complexe carbonaté extrèment stable en milieu naturel. Les expériences de terrain réalisées ont prouvé l'efficacité de ces traceurs et confirmé leur grande stabilité.

Les courbes de restitution obtenues ont montré que, conformément à nos hypothèses, la convection et la dispersion sont identiques pour l'ensemble de ces éléments. De plus, il a été établi une relation directe entre leurs taux de fixation sur le terrain et la valeur de leurs constantes de stabilité.

On dispose ainsi d'une possibilité de multitraçage corrélatif, avec des relations interélémentaires connues et quantifiables.     

Seasonal snowline instability in an energy balance model

The stability properties of a seasonal, one dimensional energy balance climate model are examined. The model contains idealized landsea geography, an interactive moving snowline and high space-time resolution. For a polar land cap surrounded by ocean we find a bifurcation in the seasonal cycle solutions as a function of solar constant leading to qualitatively different climate regimes: one with continental snow-free summers and the other with perennial snow cover over a large area surrounding the pole. In the parameterspace neighborhood of a bifurcation an infinitesimal change in any radiation budget parameter can cause the transition from one state to the other. Of special interest to those planning more elaborate numerical experiments (GCMs) is the result that 10s of seasonal cycles may be necessary for the model to damp out transient effects before settling upon a repeating seasonal cycle if parameter values are such that the solution is near a bifurcation. This latter finding is unexpected, since the longest time scale in the linear version of the energy balance model is about 5 years.     

Fluid fluxes during low-temperature alteration: implications of multi-style alteration assemblages from the Welsh Borderland,UK

Localized (domainal) low-temperature alteration may indicate variations in the chemistry of alteration fluids and/or discrete fluid flow paths during metamorphism. Occurrences of epidote- and pumpellyite-dominated domains are often used as evidence for large fluxes of Ca-rich fluids. However, comparative studies of two domainal alteration styles from basaltic to andesitic lavas and volcaniclastic rocks at Builth Wells, Wales, UK suggest that such interpretations cannot be applied universally. Here, only one set of domains can be attributed to large fluxes of Ca-rich fluids. In contrast, the second set of domains formed where the host rock supplied the necessary Ca, and fluid/rock ratios were relatively low. These domains are hosted by rocks which show a Caledonian regional metamorphic imprint, characterized by the alteration assemblage albite+chlorite+titanite±prehnite±pumpellyite±calcite±muscovite±quartz (considered to have formed at c. 200°C and ≤2.5 kbar). Type 1 domains lie along fluid channelways, such as veins. Pumpellyite is the dominant secondary mineral, but the alteration assemblage is variable with pumpellyite±prehnite±calcite±titanite±chlorite (±quartz). The domains formed at temperatures of 130–230°C during Ordovician hydrothermal activity, before the peak of regional metamorphism. In contrast, Type 2 domains are not associated with obvious fluid channelways. A central prehnite-dominated zone typically has a rim with the assemblage pumpellyite+calcite±prehnite±chlorite±titanite±K-rich phyllosilicate. These domains probably formed from pelitic xenoliths which contained a volcaniclastic component at temperatures of 130–230°C and at relatively low fluid/rock ratios. However, the timing of domain formation is uncertain. Pyrobitumen, in veins and disseminated throughout the rock, may have influenced the formation of both types of domain by stabilizing pumpellyite in preference to epidote and causing metamorphic calcite formation through the release of CO₂ to the alteration fluids. © 1996 John Wiley & Sons, Ltd.