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 iron-isotope fractionation dictated by the carboxylic functional: An ab-initio investigation

The ground-state geometries, electronic energies and vibrational properties of carboxylic complexes of iron were investigated both in vacuo and under the effect of a reaction field, to determine thermodynamic properties of iron-acetates and the role of the carboxylic functional on the isotopic imprinting of this metal in metalorganic complexation. The electronic energy, zero point corrections and thermal corrections of these substances at variational state were investigated at the DFT/B3LYP level of theory with different basis set expansions and the effect of the reaction field on the variational structures was investigated through the Polarized Continuun Model. Thermochemical cycle calculations, combined with solvation energy calculations and appropriate scaling from absolute to conventional properties allowed to compute the Gibbs free energy of formation from the elements of the investigated aqueous species and to select the best procedure to be applied in the successive vibrational analysis. The best compliance with the few existing thermodynamic data for these substances was obtained by coupling the gas phase calculations at DFT/B3LYP level with the [6-31G(d,p)]-[6-31G+(d,p)] (for cations and neutral molecules - anions; respectively) with solvation calculations adopting atomic radii optimized for the HF/6-31G(d) level of theory (UAHF). A vibrational analysis conducted on ⁵⁴Fe, ⁵⁶Fe, ⁵⁷Fe and ⁵⁸Fe gaseous isotopomers yielded reduced partition function ratios which increased not only with the nominal valence of the central cation, as expected, but, more importantly, with the extent of the complexation operated by the organic functional. Coupling thermodynamic data with separative effects it was shown that this last is controlled, as expected, by the relative bond strength of the complex in both aggregation states. Through the Integral Equation Formalism of the Polarized Continuum Model (IEFPCM) the effect of the ionic strength of the solution and of a T-dependent permittivity on the energy and separative effects of the solvated metalorganic complexes were analyzed in detail. The solvent effect in the standard state (hypothetical one-molal solution referred to infinite dilution; T = 298.15 K, P = 1 bar) is a limited reduction of the separative effects of all the isotopomeric couples. With an increase in T (and the concomitant decrease in the dielectric constant of the solvent) this effect diminishes progressively.     

Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations

Recent discoveries demonstrate that the chemistry of arsenic in sulfidic waters is much more complex that previously believed. One implication is that all earlier thermodynamic data on stabilities of As thioanions require revision. Previously used experimental approaches for determining As thioanion stabilities may be inadequate to deal with the full range of complexity. Here we use computational as well as empirical information to construct a provisional model for equilibrium As thioanion distributions in sulfidic waters. Whereas previous authors have argued for either As(III) or As(V) thioanions, the new model predicts that both are important and can occur simultaneously under commonly encountered pH and ΣS^−II conditions. At the order of magnitude level, the model reasonably predicts the solubility of As₂S₃ in sulfidic solutions, provides tentative peak assignments for published Raman spectroscopic data and plausibly accounts for how sulfide modifies the bacterial toxicity of As. The model yields a thermodynamic justification for how sulfide, which is usually regarded as a reducing agent, can counter-intuitively drive oxidation of As(III) to As(V), as has been observed both in the laboratory and in the field. Despite its uncertain accuracy, the model serves as a useful source of new, testable hypotheses about As geochemistry and highlights crucial experimental data needs.     

Spatial Variability of Rock Depth in Bangalore Using Geostatistical, Neural Network and Support Vector Machine Models

Geospatial technology is increasing in demand for many applications in geosciences. Spatial variability of the bed/hard rock is vital for many applications in geotechnical and earthquake engineering problems such as design of deep foundations, site amplification, ground response studies, liquefaction, microzonation etc. In this paper, reduced level of rock at Bangalore, India is arrived from the 652 boreholes data in the area covering 220 km². In the context of prediction of reduced level of rock in the subsurface of Bangalore and to study the spatial variability of the rock depth, Geostatistical model based on Ordinary Kriging technique, Artificial Neural Network (ANN) and Support Vector Machine (SVM) models have been developed. In Ordinary Kriging, the knowledge of the semi-variogram of the reduced level of rock from 652 points in Bangalore is used to predict the reduced level of rock at any point in the subsurface of the Bangalore, where field measurements are not available. A new type of cross-validation analysis developed proves the robustness of the Ordinary Kriging model. ANN model based on multi layer perceptrons (MLPs) that are trained with Levenberg–Marquardt backpropagation algorithm has been adopted to train the model with 90% of the data available. The SVM is a novel type of learning machine based on statistical learning theory, uses regression technique by introducing loss function has been used to predict the reduced level of rock from a large set of data. In this study, a comparative study of three numerical models to predict reduced level of rock has been presented and discussed.     

AERIAL SURVEY: COLONY OF HONG KONG

This paper describes the planning and implementation of a very extensive aerial survey contract undertaken by Hunting Surveys on behalf of the Hong Kong Government. From photography carried out during January and February 1963, photogrammetric plotting at 1 : 600 and 1 : 1200 proceeded steadily over a period of 5 years to the point where all but the highest land in the Colony had been surveyed at one or other of these two large scales. The problems arising from the rather unique terrain conditions and the urban and industrial development of Hong Kong are dealt with mainly from the photographic and photogrammetric aspect but reference is made to the contribution of the Crown Lands and Survey Office of the Public Works Department of Hong Kong, who provided all ground control and undertook field verification.     

THE LAUSANNE CONGRESS

The International Society for Photogrammetry held the Xlth International Congress at Lausanne during July 1968. The authors review the activities of five of the seven I.S.P. Commissions.     

A Study of the Strathcona Mine and Its Bearing on the Origin of the Nickel-Copper Ores of the Sudbury District, Ontario

The Strathcona iron-nickel-copper sulfide ore deposit lies atthe base of the Sudbury Nickel Irruptive along the north rimof the Sudbury basin. In the vicinity of the deposit the mainbody of the Nickel Irruptive consists of an upper unit of 3700ft (1200 m) of granophyre (the ‘micropegmatite’)and a lower unit of 1500 ft (500 m) of augite norite (the ‘felsicnorite’) separated by 300 ft (100 m) of transitional rock(the ‘transition zone’). Two augite norite intrusions(the ‘mafic norite’ and the ‘xenolithic norite’)that are younger than the felsic norite occur along its lowercontact. The xenolithic norite is relatively rich in xenolithsand grades downwards into a unit known as the ‘hanging-wallbreccia’. The breccia resembles the xenolithic noritebut contains a higher proportion of xenoliths. A quartz-plagioclase-augite gneiss (the ‘footwall gneiss’)underlies all units of the Nickel Irruptive. A cataclastic breccia(the ‘footwall breccia’) which formed as a resultof comminution of both gneiss and overlying Irruptive rocksis present in most areas between the gneiss and the Nickel Irruptive.The ore body occurs partly as a dissemination of sulfides inthe matrix of the hanging-wall breccia (‘hanging-wallore’), partly as a fine dissemination and massive stringersof sulfide in the footwall breccia matrix (‘main-zoneore’), and partly as massive stringers of sulfide in thefootwall gneiss (‘deep-zone ore’). Xenoliths in the xenolithic norite and hanging-wall brecciarange from dunite to olivine gabbro. Olivine in the xenoliths(composition estimated by an X-ray method) varies from Fo73to Fo85, and hypersthene and augite (composition estimated byelectron microprobe analysis) vary from Fs25 to Fsi3, and Fsi3to Fs5, respectively. The iron content of the mafic mineralsshows a positive correlation with the proportion of felsic mineralsin the xenoliths, suggesting that the xenoliths have been derivedfrom a cryptically layered body of mafic and ultramafic rock.The wide distribution of xenoliths around the margin of theNickel Irruptive coupled with the absence of any obvious externalsource is strong evidence that the xenoliths are cognate, supportingWilson's (1956) proposal that the Irruptive is a funnel-shapedintrusion with a zone of ultramafic rocks towards its base. Hypersthene ranges from Fs33 to Fs28 in the felsic norite, fromFs28 to Fs22 in the mafic norite, and from Fs28 to Fs20 in thexenolithic norite. Augite ranges from Fsl6 to Fs14 in the felsicnorite and from Fs14 to Fsn in both the mafic and xenolithicnorites. The distribution coefficient for iron and magnesiumbetween coexisting augite and hypersthene ranges from 1-0 insome of the xenoliths to 1-5 in some samples of felsic norite,indicating that the two pyroxenes equilibrated at, or near,magmatic temperature. The composition of plagioclase in thefelsic norite, mafic norite, and xenolithic norite is aroundAn65-70 but decreases to An44 in those Irruptive rocks closestto the footwall breccia. The composition of plagioclase withinthe breccia varies between An32 and An43. Sodium metasomatismappears to have affected the breccia and to have spread outto affect adjacent rocks. The concentration of nickel and copper in the sulfides variessystematically across the ore deposit. The nickel content ofiron-nickel sulfides varies between 2-5 and 3 per cent in thehanging-wall ore but increases regularly from 3 per cent to5 or 5-5 per cent from hanging wall to footwall across the main-zoneore. Copper concentration shows a similar but more erratic variation.The variation is attributed to thermal diffusion of nickel andcopper within the main-zone ore along a gradient induced bythe overlying, hot, Nickel Irruptive. The principal opaque minerals in the ore body are, in the orderof their abundance, pyrrho-tite of at least two types, magnetite,pentlandite, chalcopyrite, and pyrite. All of the sulfides inthe hanging-wall ore are the result of exsolution from a high-temperature,pyrrhotite solid solution. Pyrite started to exsolve below 700C, chalcopyrite below 450 C, and pentlandite below 300 C.Monoclinic pyrrhotite formed from the host hexagonal pyrrhotiteprobably between 300 and 250 C. The temperature of formationof the sulfides in the main-zone ore has been obscured by reworkingof the ore after its first emplacement. The principal ore sulfides, pyrrhotite and pentlandite, arecommon throughout the mafic norite, xenolithic norite, and hanging-wallbreccia, occurring in amounts around 5 per cent in most samples.Pyrrhotite and pentlandite are extremely rare in the overlyingfelsic norite where pyrite is the most common sulfide. It occursin amounts between 01 and 0-5 per cent, commonly together withsecondary amphibole after pyroxene. The sulfides in the maficand xenolithic norites and in the hanging-wall breccia occupyspaces interstitial to the silicates, and little or no replacementof silicates by sulfides has occurred. In the main-zone ore,evidence of small-scale replacement of silicates by sulfidesis common. The high percentage of pyrrhotite and pentlandite in the maficand xenolithic norites in contrast to the felsic norite, texturalrelations between sulfides and silicates, and the high temperaturesindicated by the pyroxene distribution coefficients lead tothe conclusion that the hanging-wall sulfides (including thehanging-wall ore) at Strathcona were introduced with these youngernoritic intrusions. Data on the solubility of sulfides in silicatemagmas rule out the possibility that the bulk of the sulfideswere in solution in the noritic magmas; the data support thehypothesis that during intrusion the sulfides were held in suspensionin the in the magmas as droplets of immiscible sulfide-oxideliquid. Calculations on the rate of settling to be expectedfor such sulfide droplets are consistent with this hypothesis.The manner of emplacement of the main-zone ore is less certain;our explanation is that this ore consists of sulfides that originallysettled out of, or collected along, the base of the hanging-wallbreccia zone and were subsequently incorporated in the brecciationthat gave rise to the footwall breccia. The origin of the sulfides at Strathcona is clearly connectedclosely with the origin of the younger noritic intrusions. Asimilar connexion exists between sulfides and young marginalintrusions at many other Sudbury deposits. Jt is possible thatboth sulfides and intrusions are portions of the Nickel Irruptivemagma that lagged behind the main body of magma and were intrudedat a later stage. Alternatively, the young intrusions may haveassimilated sulfides from a sulfide-rich zone within or at themargin of the deeper layers of the Irruptive.     

Prediction of the field strength fading forms by means of weather situations

Summary In this study the different forms of the electromagnetic field strength recordings at the Thera-Crete microwave line of link are examined, in comparison with the corresponding weather situations prevailing over that area. According to the amplitude of fluctuations, the different forms of recordings have been classified in three basic typesA, B, C and the annual frequency of the appearance of these types has been observed. Finally, the influence of weather situations on radio wave propagation was examined and it has been found that in most cases a close relationship exists between weather situations and the different fading forms of the electromagnetic field so that a prediction of the fading form be possible by means of the weather forecast.This study was sponsored by a research grant from NATO's Scientific Committee.     

Untersuehungen an den Sedimenten der Tongrube von Willershausen

Zusammenfassung Nach der Profilaufnahme sind die Sedimente der Tongrube der Ziegelei von Willershausen in zwei Gruppen einzuteilen : A. Die unteren hellen Schichten, B. die oberen dunklen Schichten.Die unteren hellen Schichten bestehen aus Sandsteinen, Sanden, tonigen Sanden und Grobtonen, welche Quarz, Feldspäte und Glimmer als Hauptminerale und in geringeren Mengen Illit, Chlorit und manchmal Montmorillonit füren. Als Schwerminerale dieser Sande und Sandsteine treten der Häufigkeit nach Apatit, Zirkon, Granat, Anatas, Rutil, Turmalin und Opakminerale auf.Die oberen dunklen Schichten bestehen hauptsächlich aus mm-rhythmisch geschichteten Tonen mit Einschaltung einzelner Mergelbänke und toniger Sandschichten. Dioktaedrischer Illit ist das häufigste Tonmineral, dann folgen Chlorit und in geringeren Mengen in feinen Fraktionen Montmorillonit. Die Chlorit-Reflexe verschwinden bereits bei Erhitzung auf 450° C. Chemisch handelt es sich um die dem Pennin naheliegenden Diabantite.Die Unterschiede in Beschaffenheit und Menge der Quarze, Feldspäte und Glimmer, die unterschiedliche Verteilung der Schwerminerale sprechen dafür, daß die hellen Schichten wahrscheinlich zum Mesozoikum, vielleicht zum Buntsandstein gehören.Von der Mathematisch-Naturwissenschaftlichen Fakultät der Georg-August-Universität zu Göttingen genehmigte Dissertation.