ToF-SIMS and SEM study on the preferential oxidation of chalcopyrite

Chalcopyrite is known to be slow reacting mineral in hydrometallurgical systems and is considered one of the most inert sulphide minerals with respect to leaching. Such character of chalcopyrite seems to be linked to a formation of a passive layer on its surface. This work reports that freshly fractured chalcopyrite surfaces exhibit highly selective reactivity depending on the exposed fracture planes. ToF-SIMS was used to qualitatively characterize various fracture planes in freshly fractured chalcopyrite particles, prior to and after hydrometallurgical treatment. It was found that, prior to treatment, certain areas exhibited pronounced contamination from atmospheric hydrocarbons; whereas, others were highly unreactive and remarkably free from adventitious hydrocarbon contamination. The positive ion spectra recorded from these areas were found to be dominated by peaks from Fe- and Cu-elements and related compounds. The negative ion spectra for the reactive areas on the other hand showed a high content of oxidized (sulphur) species.The differences between the areas of low and high reactivity, as detected after leaching, were more subtle than prior to leaching; whereas, SEM analysis showed clear evidence for selective attack of ferric sulphate to specific planes. Furthermore, it was shown that, when chalcopyrite is in intimate contact with pyrite, it experiences an enhanced oxidation compared to when there is no electric contact with pyrite.Attempts were made to explain the preferential oxidation observed based on the different chemistry of the fracture surfaces.     

Assessment of long-range kinematic GPS positioning errors by comparison with airborne laser altimetry and satellite altimetry

Long-range airborne laser altimetry and laser scanning (LIDAR) or airborne gravity surveys in, for example, polar or oceanic areas require airborne kinematic GPS baselines of many hundreds of kilometers in length. In such instances, with the complications of ionospheric biases, it can be a real challenge for traditional differential kinematic GPS software to obtain reasonable solutions. In this paper, we will describe attempts to validate an implementation of the precise point positioning (PPP) technique on an aircraft without the use of a local GPS reference station. We will compare PPP solutions with other conventional GPS solutions, as well as with independent data by comparison of airborne laser data with “ground truth” heights. The comparisons involve two flights: A July 5, 2003, airborne laser flight line across the North Atlantic from Iceland to Scotland, and a May 24, 2004, flight in an area of the Arctic Ocean north of Greenland, near-coincident in time and space with the ICESat satellite laser altimeter. Both of these flights were more than 800 km long. Comparisons between different GPS methods and four different software packages do not suggest a clear preference for any one, with the heights generally showing decimeter-level agreement. For the comparison with the independent ICESat- and LIDAR-derived “ground truth” of ocean or sea-ice heights, the statistics of comparison show a typical fit of around 10 cm RMS in the North Atlantic, and 30 cm in the sea-ice region north of Greenland. Part of the latter 30 cm error is likely due to errors in the airborne LIDAR measurement and calibration, as well as errors in the “ground truth” ocean surfaces due to drifting sea-ice. Nevertheless, the potential of the PPP method for generating 10 cm level kinematic height positioning over long baselines is illustrated.     

Mineral Paragenesis of the Lepanto Copper and Gold and the Victoria Gold Deposits, Mankayan Mineral District, Philippines

Abstract: Mineral paragenesis of the alteration, ore and gangue minerals of the Lepanto epithermal copper‐gold deposit and the Victoria gold deposit, Mankayan Mineral District, Northern Luzon, Philippines, is discussed. The principal ore minerals of the Lepanto copper‐gold deposit are enargite and luzonite, with significant presence of tennantite‐tetrahedrite, chalcopyrite, sphalerite, galena, native gold/electrum and gold‐silver tellurides. Pervasive alteration zonations are commonly observed from silicification outward to advanced argillic then to propylitic zone. The ore mineralogy of the Lepanto copper‐gold deposit suggests high f_S2 in the early stages of mineralization corresponding to the deposition of the enargite‐luzonite‐pyrite assemblage. Subsequent decrease in the f_S2 formed the chalcopyrite‐tennantite‐pyrite assemblage. An increase in the f_S2 of the fluids with the formation of the covellite‐digenite‐telluride assemblage caused the deposition of native gold/electrum and gold‐silver tellurides. The principal ore minerals of the Victoria gold deposit are sphalerite, galena, chalcopyrite, tetrahedrite and native gold/electrum. The alteration halos are relatively narrow and in an outward sequence from the ore, silica alteration grades to illitic‐argillic alteration, which in turn grades to propylitic alteration. The Victoria gold mineralization has undergone early stages of silica supersaturation leading to quartz deposition. Vigorous boiling increased the pH of the fluids that led to the deposition of sulfides and carbonates. The consequent decrease in H₂S precipitated the gold. Gypsum and anhydrite mainly occur as overprints that cut the carbonate‐silica stages. The crosscutting and overprinting relationships of the Victoria quartz‐gold‐base metal veins on the Lepanto copper‐gold veins manifest the late introduction of near neutral pH hydrothermal fluids.     

Collision, subduction and accretion events in the Philippines: A synthesis

Abstract The Philippines preserves evidence of the superimposition of tectonic processes in ancient and present‐day collision and subduction zone complexes. The Baguio District in northern Luzon, the Palawan–Central Philippine region and the Mati–Pujada area in southeastern Mindanao resulted from events related to subduction polarity reversal leading to trench initiation, continent‐arc collision and autochthonous oceanic lithosphere emplacement, respectively. Geological data on the Baguio District in Northern Luzon reveal an Early Miocene trench initiation for the east‐dipping Manila Trench. This followed the Late Oligocene cessation of subduction along the west‐dipping proto‐East Luzon Trough. The Manila Trench initiation, which is modeled as a consequence of the counter‐clockwise rotation of Luzon, is attributed to the collision of the Palawan microcontinental block with the Philippine Mobile Belt. In the course of rotation, Luzon onramped the South China Sea crust, effectively converting the shear zone that bounded them into a subduction zone. Several collision‐related accretionary complexes (e.g. Romblon, Mindoro) are present in the Palawan–Central Philippine region. The easternmost collision zone boundary is located east of the Romblon group of islands. The Early Miocene southwestward shift of the collision boundary from Romblon to Mindoro started to end by the Pliocene. Continuous interaction between the Palawan microcontinental block and the Philippine Mobile Belt is presently taken up again along the collisional boundary east of the Romblon group of islands. The Mati–Pujada Peninsula area, on the other hand, is underlain by the Upper Cretaceous Pujada Ophiolite. This supra‐subduction zone ophiolite is capped by chert and pelagic limestones which suggests its derivation from a relatively deep marginal basin. The Pujada Ophiolite could be a part of a proto‐Molucca Sea plate. The re‐interpretation of the geology and tectonic settings of the three areas reaffirm the complex geodynamic evolution of the Philippine archipelago and addresses some of its perceived geological enigmas.     

Thermal history,hydrocarbon generation and migration in the Horn Graben in the Danish North Sea: a 2D basin modelling study

In this study a 2D basin model has been built along a transect crossing the Horn Graben in WNW-ESE direction. The aim of the investigation was to improve the understanding of the thermal evolution of the basin and its influence on possible petroleum systems. The 2D model of the subsurface is based on one seismic line and data from two exploration wells. Both wells TD’ed in Triassic sediments. The updoming of the Ringkøbing-Fyn High began during Late Carboniferous–Early Permian. At the end of the Permian the Horn Graben became active due to regional extension. The subsequent sedimentation history from Triassic to date is well recorded by well reports. A matter of debate has been whether or not significant amounts of Pre-Permian sediments exist in this area of the North Sea. Since organic material rich Paleozoic sediments serve as source rocks in widespread areas of North Germany and the southern North Sea it would be of great importance to know whether the same deposits exist in the Horn Graben. Nielsen et al. (Bull Geol Soc Denmark Copenhagen 45:1–10, 1998) introduced a model, which shows Paleozoic sediments covering the basement at a maximum depth of 6.5 km. Assuming, Paleozoic sediments are underlying the Permian salt deposits there should be an active petroleum system present. The 2D model includes the Paleozoic source rock and tries to explain why two exploration wells have not found petroleum.     

A statistical test on the local effects of spatially structured variance

Spatial variance is an important characteristic of spatial random variables. It describes local deviations from average global conditions and is thus a proxy for spatial heterogeneity. Investigating instability in spatial variance is a useful way of detecting spatial boundaries, analysing the internal structure of spatial clusters and revealing simultaneously acting geographic phenomena. Recently, a corresponding test statistic called ‘Local Spatial Heteroscedasticity’ (LOSH) has been proposed. This test allows locally heterogeneous regions to be mapped and investigated by comparing them with the global average mean deviation in a data set. While this test is useful in stationary conditions, its value is limited in a global heterogeneous state. There is a risk that local structures might be overlooked and wrong inferences drawn. In this paper, we introduce a test that takes account of global spatial heterogeneity in assessing local spatial effects. The proposed measure, which we call ‘Local Spatial Dispersion’ (LSD), adapts LOSH to local conditions by omitting global information beyond the range of the local neighbourhood and by keeping the related inferential procedure at a local level. Thereby, the local neighbourhoods might be small and cause small-sample issues. In the view of this, we recommend an empirical Bayesian technique to increase the data that is available for resampling by employing empirical prior knowledge. The usefulness of this approach is demonstrated by applying it to a Light Detection and Ranging-derived data set with height differences and by making a comparison with LOSH. Our results show that LSD is uncorrelated with non-spatial variance as well as local spatial autocorrelation. It thus discloses patterns that would be missed by LOSH or indicators of spatial autocorrelation. Furthermore, the empirical outcomes suggest that interpreting LOSH and LSD together is of greater value than interpreting each of the measures individually. In the given example, local interactions can be statistically detected between variance and spatial patterns in the presence of global structuring, and thus reveal details that might otherwise be overlooked.     

Structure of the Mid Atlantic Ridge province between 12° and 18°N

An analysis is given of air-gun profiler and magnetic data obtained in the central North Atlantic between 12° and 18°N. Eight fracture zones were crossed, one of which (the 15°20N fracture zone) was traced over a distance of 1500 km. The mode of adjustment of fracture zones to a change in direction of spreading is discussed. It is shown that also if this new direction would lead to an opening of the fracture zone, and adjustment fracture can originate and actually does so in several instances.The about E-W fracture zones dominate the structure of the Ridge province entirely, both with regard to the topography and to the magnetics. A magnetic model is proposed accounting for the different types of anomalies found over fracture zones. No intrusive bodies are needed to explain these anomalies.The origin of fracture zones is related to thermal contraction of a cooling lithosphere while moving from the ridge. Thermal contraction may also explain how the American and the African plates are freed from the grip they are caught in by the fanning of the fracture zones in the central North Atlantic. The fanning of fracture zones has consequences for the determination of the pole of spreading. This pole can only be found as a best fit from a synthesis of the total plate boundary, i.e. from the Azores to Bouvet Island. Local poles have only restricted value, since deviations up to 5 deg occur from a small circle pattern based on existing data.Several huge structures, viz. Researcher Ridge and Royal Trough, are found in the area which seem to parallel the flow lines of the fracture zone system. No adequate explanation exists for these structures.     

Volatile organic compounds in coastal seawater

The occurence and temporal variations of a variety of low to medium polarity organic compounds in the volatility range bracketed by n-heptane and n-octadecane have been studied in seawater from a station in Vineyard Sound, Massachusetts, and from a tidal creek in Sippewisset Marsh, Massachusetts. The closed-loop vapor phase stripping method of Grob and Zürcher (J. Chromatogr., v. 117, p. 285–294), high resolution glass capillary gas chromatography, and gas chromatography-mass spectrometry were used. Approximately 50 compounds were found at ≥ 2 ng/kg; most were recovered at less than 10 ng/kg, while the 20 ng/kg level was only rarely exceeded by a few components. The total material recovered was 0.2–1.0 μg organic carbon equivalent/kg seawater. The major compound classes found were normal alkanes, alkenes, aromatic and alkylaromatic hydrocarbons, n-aldehydes, dimethyldisulfide and dimethyltrisulfide, and a few halogenated hydrocarbons. The preliminary results suggest that both biogenic and anthropogenic sources were representted. Also, air-sea gas exchange and other physical processes may be important non-biological sinks.     

Empirical NLTE analyses of solar spectral lines

The center-to-limb behaviour of the Ba ii 4554 resonance line is analyzed together with data from the extreme limb, flash intensities and profiles of other Ba ii lines. An empirical NLTE method is employed in which the observed profiles are compared with synthesized profiles based on a standard one-dimensional model atmosphere, with the line source function, the barium abundance, the collisional damping and the atmospheric turbulence as free parameters.The line profiles from the extreme limb furnish considerable constraints on the formation of Ba ii 4554. Its wings reverse into emission well inside the solar limb, a phenomenon which cannot be explained by any frequency-independent line source function. Accounting for effects of partially coherent scattering in the line source function is a necessary and adequate step to reproduce the observations both over the disk and near the limb. The form of the empirically derived frequency-dependent line source function is discussed.Results are given for various parameters (gf-values, solar barium abundance and isotope ratios, collisional damping, microturbulence and macroturbulence).The 4554 profile of disk center shows a depression in its blue wing resembling asymetries found in various stellar spectral lines.