The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

Models of aggradation versus progradation in the Himalayan Foreland

A frequent goal of decompaction analysis is to reconstruct histories of basin subsidence and tectonic loading. In marine environments, eustatic and paleobathymetric uncertainties limit the resolution of these reconstructions. Whereas in the terrestrial basins, these ambiguities are absent, it is still necessary to account for depositional slopes between localities in order to analyze three-dimensional patterns of subsidence. We define two end-members for depositional surfaces: aggradation and progradation. The relative importance of either end-member is a function of the interplay between the rate of net sediment accumulation and the rate of basin subsidence. The models predict the patterns of major drainages (transverse versus longitudinal) and the way in which provenance should be reflected within different portions of a basin. Consequently, paleocurrent and provenance data from the ancient stratigraphic record can be used to distinguish between these endmembers. The subhorizontal depositional surfaces that dominate during times of aggradation provide a well defined reference frame for regional analysis of decompacted stratigraphies and related subsidence. Depositional slopes during progradation can not be as precisely specified, and consequently yield greater uncertainties in reconstructions of subsidence. These models are applied to the Mio-Pliocene foreland basin of the northwestern Himalaya, where sequences of isochronous strata have been analyzed throughout the basin. These time-controlled data delineate a distinctive evolution from largely aggradational to largely progradational depositional geometries as deformation progressively encroaches on the foreland. Such a reconstruction of past depositional surfaces provides a well constrained reference frame for subsequent integration of subsidence histories from throughout the foreland.

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Zusammenfassung Ein häufiges Ziel der Dekompaktionsanalyse ist es die Beckenabsenkung und die tektonische Belastung zu rekonstruieren. In marinen Ablagerungsräumen limitieren eustatische und paläobathymetrische Unsicherheiten die Auflösung der Rekonstruktion. Bei terrestrischen Becken fehlen diese Zweideutigkeiten; es ist aber trotzdem notwendig, Rechenschaft über den Ablagerungshang zwischen verschiedenen Lokalitäten abzulegen, um dreidimensionale Subsidenzmuster zu analysieren. Wir definieren zwei Endglieder von Ablagerangsflächen: Aggradation und Progradation. Die relative Wichtigkeit des jeweiligen Endglieds ist eine Funktion des Zusammenspiels zwischen der Nettorate der Sedimentakkumulation und der Beckensubsidenz. Die Modelle sagen die Hauptentwässerungsmuster (quer- oder längsverlaufend) vorher, sowie den Weg in dem die Sedimentherkunft innerhalb verschiedener Bereiche des Beckens berücksichtigt werden sollte. Folglich können Paläoströmungs- und Herkunftsdaten alter stratigraphischer Überlieferungen benutzt werden, um zwischen den Endgliedern zu unterscheiden. Die subhorizontale Ablagerungsfläche welche zur Zeit der Aggradation dominant ist, liefert einen gut definierten Referenzrahmen für die regionale Analyse von dekomprimierten Formationen und der damit verknüpften Subsidenz. Ablagerangshänge während Progradation können nicht präzise spezifiziert werden und beinhalten daher größere Unsicherheiten bei der Rekonstruktion der Subsidenz. Diese Modelle wurden übertragen auf das miozäne bis pliozäne Vorgebirgsbecken des nordwestlichen Himalayas, wo Sequenzen von isochronen Schichten durch das gesamte Becken analysiert werden konnten. Diese zeitkontrollierten Daten schildern eine ganz bestimmte Entwicklung, die von einer hauptsächlich aggradierenden zu einer progradierenden Ablagerangsgeometrie verlief, während der die Deformation schrittweise in Richtung Vorland übergriff. Diese Rekonstruktion von ehemaligen Ablagerangsflächen liefert einen guten Referenzrahmen für die folgende Integration der Subsidenzgeschichte des gesamten Vorlands.

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Résumé L'analyse de décompaction a souvent pour but de reconstituer l'histoire de la subsidence d'un bassin et de la charge tectonique. Dans les milieux marins, de telles reconstitutions sont limitées par des incertitudes de caractère eustatique et paléobathymétrique. Par contre, ces ambiguïtés ne se présentent pas dans le cas des bassins continentaux, où il convient néanmoins de tenir compte de la pente de la surface de dépôt entre les divers points considérés pour établir un schéma tridimensionnel de la subsidence. Nous définissons deux situations extrêmes pour les surfaces de dépôt: l'aggradation et la progradation. L'importance relative de ces deux extrêmes est fonction de l'interaction entre le taux d'accumulation net des sédiments et le taux de subsidence du bassin. Les modèles prévoient la répartition des drainages principaux (transverse ou longitudinal) et la manière dont l'origine des sédiments peut se répercuter dans les diverses parties d'un bassin. Il en résulte que des informations fournies par les relevés stratigraphiques à propos des paléocourants et de la source des sédiments peuvent être utilisées pour faire la distinction entre les deux cas extrêmes. Les surfaces de dépôt subhorizontales, qui prédominent pendant les périodes d'aggradation, fournissent un bon cadre de référence pour les analyses régionales de formations décompactées et de la subsidence qui leur est associée. Les surfaces de dépôt inclinées qui se présentent au cours des progradations ne peuvent pas être définies de manière aussi précise et engendrent par conséquent plus d'incertitude dans la reconstitution de la subsidence. Les auteurs appliquent ces modèles au bassin mio-pliocène d'avant-pays de l'Himalaya nord-occidental, dans lequel des séquences de couches isochrones ont été suivies à travers tout le bassin. Ces données, chronologiquement définies, fournissent l'image d'une évolution nette, depuis des géométries typiques d'aggradation jusqu' à des géométries typiques de progradation, au fur et à mesure de l'emprise progressive de la déformation sur l'avant-pays. Une telle reconstitution des surfaces de dépôt anciennes fournit un bon cadre de référence en vue de l'intégration ultérieure de l'histoire de la subsidence dans l'ensemble de l'avant-pays.

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Astrometric investigation with the Tautenburg Schmidt telescope

The observations and the plate reduction technique for the determination of positions and absolute proper motions which is used in Potsdam are described. Recent results have shown that an accuracy of about 0 _. 1 for positions and 0 _. ⁷ cent _. ^–1 for proper motions can be achieved both for bright (8^m–12^m) and faint (16^m–18^m) stars. Three astrometric programmes using the Tautenburg plates are presented.     

Preliminary observations of solar radio sources with the Culgoora radioheliograph operating at four frequencies

The Culgoora radioheliograph has been modified for observing at 327.4 MHz, which is in addition to the three frequencies (43.25, 80, and 160 MHz) previously available. At the new frequency the array beamwidth is 56, which represents the highest resolution yet available for metre-wavelength solar mapping.At 327.4 MHz the sources of radio emission are mainly in the lowest layers of the corona. Some preliminary four-frequency observations have been made of type I storms. It is found that the source size generally decreases with increasing observing frequency. This result confirms earlier suggestions that the sources of both type I and type III emission are contained in structures whose boundaries diverge outwards in the corona.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

The Fe-C system at 5 GPa and implications for Earth’s core

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.     

THE AIR PHOTOGRAPH REQUIREMENTS OF GEOLOGISTS

The geologist's use of air photographs and the characteristics studied by photogeologists are briefly described. The influence of photographic factors such as scale, season, time of day, film type, processing, overlap and dimensional accuracy are considered from the geologist's viewpoint.     

THE ANALYTICAL ORIENTATION OF A LUNAR MODEL

An analytical relative orientation of a stereo-pair of photographs was computed in an unusual system of co-ordinates. The disparity in the widely mismatched photographs, their tilts and narrow angles subtended resulted in a rather weak solution from which sections of the lunar surface have been plotted. The results were not good but were better than expected. The main outcome of the work is a, probably unique, demonstration of the versatility of analytical photogrammetry.