Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.     

Application of Hilbert‐like transforms for enhanced processing of full tensor magnetic gradient data

Commonly, geomagnetic prospection is performed via scalar magnetometers that measure values of the total magnetic intensity. Recent developments of superconducting quantum interference devices have led to their integration in full tensor magnetic gradiometry systems consisting of planar‐type first‐order gradiometers and magnetometers fabricated in thin‐film technology. With these systems measuring directly the magnetic gradient tensor and field vector, a significantly higher magnetic and spatial resolution of the magnetic maps is yield than those produced via conventional magnetometers. In order to preserve the high data quality in this work, we develop a workflow containing all the necessary steps for generating the gradient tensor and field vector quantities from the raw measurement data up to their integration into high­resolution, low­noise, and artefactless two‐dimensional maps of the magnetic field vector. The gradient tensor components are processed by superposition of the balanced gradiometer signals and rotation into an Earth‐centred Earth‐fixed coordinate frame. As the magnetometers have sensitivity lower than that of gradiometers and the total magnetic intensity is not directly recorded, we employ Hilbert‐like transforms, e.g., integration of the gradient tensor components or the conversion of the total magnetic intensity derived by calibrated magnetometer readings to obtain these values. This can lead to a better interpretation of the measured magnetic anomalies of the Earth's magnetic field that is possible from scalar total magnetic intensity measurements. Our conclusions are drawn from the application of these algorithms on a survey acquired in South Africa containing full tensor magnetic gradiometry data.     

Areal extent of the 1988 flood in Bangladesh: How much did the satellite imagery show?

This paper presents the methods and results of visual interpretation of satellite imagery for estimating areal extent of the 1988 flood in Bangladesh. The main limitation of this method was that cloud-free images were not available for the peak flood period in the first week of September. Relatively cloud-free images on three selected dates in the last three weeks of September showed that areas of inundation on those dates ranged from 44000 to 60000 km² ± 5% (31 to 42% of Bangladesh). The Government of Bangladesh official estimates of the areal extent of flooding were tentative in nature, since these were based on a choropleth map of relative proportions (percentages) of flooding in different parts of the country. The official estimate of the maximum extent of flooding was 82000 km² (57% of Bangladesh), i.e. 15 to 26% larger than the area shown on satellite imagery. The actual extent of flooding was certainly larger than the estimates from satellite imagery but, perhaps, smaller than the official estimates, since a reduction of 15 to 26% of flood area in one to three weeks seemed unlikely. An alternative method of mapping flood-affected areas by using newspaper-interpreted data was attempted, but the method had limited values because of reporting bias.     

Acid mine drainage at Cerro Rico de Potosí I: unabated high-strength discharges reflect a five century legacy of mining

Intensive mining and processing of Ag, Sn, Pb and Zn ores have occurred in various locations within and around the city of Potosí, Bolivia since 1545. Surface and subsurface waters, stream sediments and soils are contaminated with various ecotoxic metals in the headwaters of the economically vital, yet highly impacted, upper Rio Pilcomayo watershed. Previous studies have documented downstream trace metal contamination, however, not addressed specific sources. The AMD discharges identified in this study help link downstream pollution to primary origins. The majority of AMD would be considered high-strength due to metal concentrations and acidity orders of magnitude greater than typical AMD. Discharges from both operating and abandoned portals as well as tailings-related deposits displayed a high degree of heterogeneity with total metal concentrations ranging from 0.11 to 7480, <0.022 to 889, <0.0006 to 65.3, <0.001 to 310, 0.12 to 72,100, 0.3 to 402, <0.012 to 34.8, and 0.24 to 19,600 mg/L of Al, As, Cd, Cu, Fe, Mn, Pb and Zn, respectively. Net acidity and pH ranged from −10 to 246,000 mg/L as CaCO₃ equivalent and 0.90–6.94 standard units, respectively. Data were gathered during two sampling events centered around the most extreme periods of the dry and wet seasons of one water-year. Loadings to local streams were marginally greater for most metals in the wet season. If observed loadings are historically representative, Cerro Rico AMD has contributed thousands of tonnes of ecotoxic metals to the upper Rio Pilcomayo over the last five centuries. Metal and hydrogen ion concentrations in the majority of AMD sampled were several orders of magnitude above discharge limits set by the Bolivian government, yet no action has historically or contemporarily been taken.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin.Part II: Substituted Phenols in Berlin Surface Water

In a surface water screening, 30 representative surface water samples collected from rivers, canals, and lakes in Berlin were investigated for the presence of 22 substituted phenols. The phenols selected include the 11 phenols considered as “priority pollutants” by the US Environmental Protection Agency (US-EPA). Surface water samples were extracted applying solid-phase extraction with styrenedivinylbenzene adsorbent. The recoveries, determined in spiking experiments, were between 80 % and 103 %. After derivatization with N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) the samples were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). Phenol, cresols, 2-ethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, 2-nitrophenol, and 4-nitrophenol were detected in the surface water samples at concentrations between 0.02 μg/L and 7.8 μg/L, respectively. The distribution of these residues in the Berlin surface waters showed that the phenolic residues, with the exception of pentachlorophenol and 2-ethylphenol, do not originate primarily from municipal sewage treatment plants discharges. Some of the phenols are formed naturally or occur as ubiquitous anthropogenic contaminants in the aquatic system.     

Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (<1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO₃^?. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO₃^?, SO₄^2?, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO₃^? (4.4 ± 2.9 mg N/L), SO₄^2? (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO₃^?‐rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley & Sons Ltd.     

Comparison of the LEW88516 and ALHA77005 martian meteorites: Similar but distinct

Abstract By mineral and bulk compositions, the Lewis Cliff (LEW) 88516 meteorite is quite similar to the ALHA77005 martian meteorite. These two meteorites are not paired because their mineral compositions are distinct, they were found 500 km apart in ice fields with different sources for meteorites, and their terrestrial residence ages are different. Minerals in LEW88516 include: olivine, pyroxenes (low- and high-Ca), and maskelynite (after plagioclase); and the minor minerals chromite, whitlockite, ilmenite, and pyrrhotite. Mineral grains in LEW88516 range up to a few mm. Texturally, the meteorite is complex, with regions of olivine and chromite poikilitically enclosed in pyroxene, regions of interstitial basaltic texture, and glass-rich (shock) veinlets. Olivine compositions range from Fo₆₄ to Fo₇₀, (avg. Fo₆₇), more ferroan and with more variation than in ALHA77005 (Fo₆₉ to Fo₇₃). Pyroxene compositions fall between En₇₇Wo₄ and En₆₅Wo₁₅ and in clusters near En₆₃Wo₉ and En₅₃Wo₃₃, on average more magnesian and with more variation than in ALHA77005. Shock features in LEW88516 range from weak deformation through complete melting. Bulk chemical analyses by modal recombination of electron microprobe analyses, instrumental neutron activation, and radiochemical neutron activation confirm that LEW88516 is more closely related to ALHA77005 than to other known martian meteorites. Key element abundance ratios are typical of martian meteorites, as is its non-chondritic rare earth pattern. Differences between the chemical compositions of LEW88516 and ALHA77005 are consistent with slight differences in the proportions of their constituent minerals and not from fundamental petrogenetic differences. Noble gas abundances in LEW88516, like those in ALHA77005, show modest excesses of ⁴⁰Ar and ¹²⁹Xe from trapped (shock-implanted) gas. As with other ALHA77005 and the shergottite martian meteorites (except EETA79001), noble gas isotope abundances in LEW88516 are consistent with exposure to cosmic rays for 2.5–3 Ma. The absence of substantial effects of shielding from cosmic rays suggest LEW88516 spent this time as an object no larger than a few cm in diameter.     

Temperature dependence of the cation distribution in nickel aluminate (NiAl2O4) spinel: a powder XRD study

NiAl₂O₄ is a largely inverse spinel, which in detail shows increasing randomisation with temperature of Ni and Al between the octahedral and tetrahedral cation sites of the spinel structure. We have used powder XRD to determine this cation distribution in various samples of NiAl₂O₄ quenched after annealing between 700 and 1400° C. The inversion parameter (x) can be measured with a precision of ± 0.004 (one standard deviation), and a comparison of different methods of synthesis, X-ray diffraction and refinement techniques, suggests a probable accuracy of better than 0.01. The results are supported by some preliminary single crystal refinements on flux-grown samples.Below 800° C the rate of cation ordering becomes very slow, and, despite reaching an apparently steady state, it is doubtful if our samples attained complete internal equilibrium. Above 1250° C the cation redistribution becomes so fast that the quenching method becomes unreliable. Between 800 and 1250° C inclusive, the degree of inversion changes smoothly from 0.87 at 800° C to 0.79 at 1250° C, and is accompanied by linear changes in u, the oxygen parameter, from 0.2555 to 0.2563 (±0.0002), and a₀, the lattice parameter, from 8.0462 to 8.0522 Å (±0.0002 Å).