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.     

AIRFLOW PATTERNS FROM PHOTOGRAMMETRIC MEASUREMENTS OF WINDBLOWN TIMBER

Aerial photography may be used to quickly locate and measure the extent and severity of forest damage due to windblow. This paper describes such an application in a small area of semi-natural woodland in central Scotland after the “Great Gale” of 14th and 15th January, 1968. A 1 : 2000 scale map, showing the location and direction of fall of each windblown tree, suggests certain relationships between topography and the severity of woodland damage and gives considerable information on the airflow pattern existing over the area during the gale.     

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.     

Stratospheric methane and nitrogen dioxide from infrared spectra

Values of the mixing ratio by volume of stratospheric NO₂ and CH₄ deduced from infrared spectra taken by means of balloon-borne spectrometers are presented. Possible evidence for the presence of formaldehyde in the stratosphere is also given.     

Deep inside a neoproterozoic intra-oceanic arc: growth,differentiation and exhumation of the Amalaoulaou complex (Gourma,Mali)

We show here that the Amalaoulaou complex, in the Pan-African belt of West Africa (Gourma, Mali), corresponds to the lower and middle sections of a Neoproterozoic intra-oceanic arc. This complex records a 90–130-Ma-long evolution of magmatic inputs and differentiation above a subducting oceanic slab. Early c. 793 Ma-old metagabbros crystallised at lower crustal or uppermost mantle depths (25–30 km) and have geochemical characteristic of high-alumina basalts extracted from a depleted mantle source slightly enriched by slab-derived sedimentary components ((La/Sm)_N < 1; ε_Nd: +5.4–6.2; ⁸⁷Sr/⁸⁶Sr: 0.7027–0.7029). In response to crustal thickening, these mafic rocks were recrystallised into garnet-granulites (850–1,000°C; 10–12 kbar) and subject to local dehydration–melting reactions, forming trondhjemititic leucosomes with garnet–clinopyroxene–rutile residues. Slightly after the granulitic event, the arc root was subject to strong HT shearing during partial exhumation (detachment faults/rifting or thrusting), coeval with the emplacement of spinel- and garnet-pyroxenite dykes crystallised from a high-Mg andesitic parental magma. Quartz and hornblende-gabbros (700–660 Ma) with composition typical of hydrous volcanic rocks from mature arcs ((La/Sm)_N: 0.9–1.8; ε_Nd: +4.6 to +5.2; ⁸⁷Sr/⁸⁶Sr: 0.7028–0.7031) were subsequently emplaced at mid-arc crust levels (~15 km). Trace element and isotopic data indicate that magmas tapped a depleted mantle source significantly more enriched in oceanic sedimentary components (0.2%). Exhumation occurred either in two stages (700–660 and 623 Ma) or in one stage (623 Ma) with a final exhumation of the arc root along cold P-T path (550°C, 6–9 kbar; epidote–amphibolite and greenschist facies conditions) during the main Pan-African collision event (620–580 Ma). The composition of magmas forming the Cryogenian Amalaoulaou arc and the processes leading to intra-arc differentiation are strikingly comparable to those observed in the deep section of exposed Mezosoic oceanic arcs, namely the Kohistan and Talkeetna complex. This evolution of the Amalaoulaou oceanic arc and its accretion towards the West African craton belong to the life and closure of the Pharusian Ocean that eventually led to the formation of the Greater Gondwana supercontinent, a similar story having occurred on the other side of the Sahara with the Mozambique Ocean.     

Experimental evaluation of biases associated with sampling estuarine fishes with seines

Beach seines are widely used to estimate the density and species richness of fishes in estuaries. We evaluated the causes and extent of bias in estimates from seines using a series of field experiments in small estuaries in southern California, USA. Seining in spatially paired areas that were either enclosed by block nets or not, revealed that seines used without block nets und erestimated density by more than 4-fold and species richness by more than 2-fold relative to blocked areas. Seining in paired blocked areas with seines of two lengths revealed that net length affected estimates of density, but not species richness; a 7.6-m long seine produced 1.6-fold higher estimates of total density than did a 15.2-m long seine due to increased catches of demersal fishes, but not midwater species. Paired sampling in blocked areas also revealed that many fishes initially evaded capture by the seine. Estimates of density but not species richness were significantly higher in areas through which a seine was swept 5 times compared to once. This was due to higher catches of demersal fishes but not midwater fishes in areas seined 5 times. Repeated seining through blocked areas revealed that the vast majority (90% or more) of species and individuals of midwater fishes were captured within the first 5 sweeps, compared to only about 50% of the individuals of demersal species. A mark-recapture study in blocked areas revealed lower probabilities of capture for demersal species relative to midwater species.     

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).     

Deep structure of the Racha earthquake source zone from seismic tomography data

The Racha earthquake of 1991 was the strongest of the earthquakes recorded in the Caucasus. It was studied by an international epicentral expedition. Unique data gathered by this expedition included records of aftershocks whose swarm was very intense. A 3-D velocity model is obtained from analysis of these data by the method of local earthquake tomography. The ancient crystalline basement and the sedimentary-volcanic Mesozoic-Cenozoic cover could be identified from cross sections of the P wave field. The eastern and western boundaries of an uplift in the basement of the Dzirulskii Massif are delineated. Linear low velocity heterogeneities correlating with the active Kakheti-Lechkhumi fault zone and two Trans-Caucasian linear fault zones are discovered in the basement. The cloud of aftershock hypocenters is shown to correlate with a reflector coinciding with the cover-basement interface.