Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

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.     

Oxygen Isotope Evidence for Chemical Interaction of Ki lauea Historical Magmas with Basement Rocks

Klauea historical summit lavas have a wide range in matrix ¹⁸O_VSMOWvalues (4·9–5·6) with lower values in rockserupted following a major summit collapse or eruptive hiatus.In contrast, ¹⁸O values for olivines in most of these lavasare nearly constant (5·1 ± 0·1). The disequilibriumbetween matrix and olivine ¹⁸O values in many samples indicatesthat the lower matrix values were acquired by the magma afterolivine growth, probably just before or during eruption. BothMauna Loa and Klauea basement rocks are the likely sources ofthe contamination, based on O, Pb and Sr isotope data. However,the extent of crustal contamination of Klauea historical magmasis probably minor (< 12%, depending on the assumed contaminant)and it is superimposed on a longer-term, cyclic geochemicalvariation that reflects source heterogeneity. Klauea's heterogeneoussource, which is well represented by the historical summit lavas,probably has magma ¹⁸O values within the normal mid-ocean ridgebasalt mantle range (5·4–5·8) based on thenew olivine ¹⁸O values. KEY WORDS: Hawaii; Klauea; basalt; oxygen isotopes; crustal contamination     

In situ strength measurements on natural upper-mantle minerals

Using in situ strength measurements at pressures up to 10 GPa and at room temperature, 400, 600, and 700°C, we examined rheological properties of olivine, orthopyroxene, and chromian-spinel contained in a mantle-derived xenolith. Mineral strengths were estimated using widths of X-ray diffraction peaks as a function of pressure, temperature, and time. Differential stresses of all minerals increase with increasing pressure, but they decrease with increasing temperature because of elastic strain on compression and stress relaxation during heating. During compression at room temperature, all minerals deform plastically at differential stress of 4–6 GPa. During subsequent heating, thermally induced yielding is observed in olivine at 600°C. Neither orthopyroxene nor spinel shows complete stress relaxation, but both retain some stress even at 700°C. The strength of the minerals decreases in the order of chromian-spinel ≈ orthopyroxene > olivine for these conditions. This order of strength is consistent with the residual pressure of fluid inclusions in mantle xenoliths.     

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.