A study of bernalite,Fe(OH)3, using Mössbauer spectroscopy,optical spectroscopy and transmission electron microscopy

To study the crystal chemistry of bernalite, Fe(OH)₃, and the nature of the octahedral Fe³⁺ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H ₀ = 55.7±0.3 T and T _N = 427±5K. The centre shift data were fitted to the Debye model with parameters ₀=0.482±0.005 mm/s (relative to -Fe) and _M=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe³⁺ at 11 300, 16000 and 23 200 cm^-1, giving a crystal field splitting of 14 570 cm^-1 and Racah parameters of B=629 cm^-1 and C=3381 cm^-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm^-1, suggesting the presence of molecular CO₂ in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe³⁺ site, and compared with values for other iron oxides and hydroxides.     

Himalayan inverted metamorphism constrained by oxygen isotope thermometry

Inverted metamorphic field gradients are preserved in two amphibolite facies metapelitic sequences forming the crystalline core zone of the Himalayan orogen in the Sutlej valley (NW India). In the High Himalayan Crystalline Sequence (HHCS), metamorphic conditions increase upwards from the staurolite zone at the base, through the kyanite-in and sillimanite-in isograds, finally to reach partial melting conditions at the top. The structurally lower Lesser Himalayan Crystalline Sequence (LHCS) shows a gradual superposition of garnet-in, staurolite-in and kyanite + sillimanite-in isograds. Although phase equilibria constraints imply inverted temperature field gradients in both units, garnet-biotite (GARB) rim thermometry indicates final equilibration at a nearly uniform temperature around T ≈ 600 °C across these sequences. The P-T path and garnet zoning data show that this apparent lack of thermal field gradient is mainly the consequence of a resetting of the GARB equilibria during cooling. In order to constrain peak temperature conditions, 20 samples along the studied section have been analysed for oxygen isotope thermometry. The isotopic fractionations recorded by quartz-garnet and quartz-aluminosilicate mineral pairs indicate temperatures consistent with phase equilibria and P-T path constraints for metamorphic peak conditions. Together with barometry results, based on net transfer continuous reactions, the oxygen isotope thermometry indicates peak conditions characterized by: (1) a temperature increase from T ≈ 570 to 750 °C at a nearly constant pressure around P ≈ 800 MPa, from the base to the top of the HHCS unit; (2) a temperature increase from T ≈ 610 to 700 °C and a pressure decrease from P ≈ 900 to 700 MPa, from the base to the top of the LHCS metapelites. Oxygen isotope thermometry thus provides the first quantitative data demonstrating that the Himalayan inverted metamorphism can be associated with a complete inversion of the thermal field gradient across the crystalline core zone of this orogen. Received: 1 April 1999 / Accepted: 12 July 1999     

Reversibility of radiocaesium sorption on illite

Adsorption of trace amounts of radiocaesium on NH₄-, K-, and Na-saturated Fithian illite and subsequent desorption by 1 M NH₄ showed that a substantial amount of radiocaesium (44%, 46%, and 91% for NH₄-, K-, and Na-illite, respectively) cannot be desorbed after only 5 min of adsorption. Our results suggest that this instantaneous fixation is caused by the collapse of the frayed edges of the clay mineral and the relatively high concentration of radiocaesium building up in solution in the batch desorption experiments. Consequently, commonly applied high-NH₄ extractions underestimate truly exchangeable amounts of radiocaesium in soils and sediments containing illitic clay minerals. The rate of desorption of trace amounts of radiocaesium from the solids using high NH₄ or Cs concentrations has a half-life of about 2 yr, reflecting radiocaesium desorption from (partially) collapsed interlayers. Extraction of radiocaesium from illite after 5 min of contact time with a Cs-selective adsorbent or a 1 × 10^-6 M CsCl solution shows that 100% of the bound radiocaesium is readily available. The desorption rate in the presence of a Cs-selective adsorbent has a half-life of about 0.2 yr. Desorption of radiocaesium from illite using different ammonium concentrations shows that radiocaesium partitioning follows reversible ion-exchange theory if the NH₄ concentration is below 1 × 10^-4 M, and sufficient time (weeks) is allowed for the reaction to proceed. Thus, radiocaesium sorption reversibility in the natural environment is much higher than generally assumed, and equilibrium solid/liquid partitioning may be assumed for the long-term modelling of radiocaesium mobility in the natural environment. In the particular case of anoxic freshwater sediments with very high NH₄ concentrations in the pore waters (up to several mmol.L^-1), collapse of the frayed edges of illite may occur, influencing radiocaesium partitioning. If collapse occurs before radiocaesium adsorbs to illite, high caesium sorption reversibility as measured by high-NH₄ extraction can be expected because further collapse of the frayed edges during the extraction procedure will be limited. This effect has indeed been observed earlier in the extraction of radiocaesium from anoxic freshwater sediments with high-NH₄ solutions and was as yet unexplained.     

Sustainability schizophrenia or “actually existing sustainabilities?” toward a broader understanding of the politics and promise of local sustainability in the US

As an approach to development, many see capitalism as reaching across an enormous range of scholarly domains and political interests. For some time geographers and others have begun to conceptualize capitalism as less of a system of intrinsic economic logic and more a collection of social and discursive relationships. By bringing capitalism into the “discursive world” these commentators and others have provided the theoretical ground for an exploration of alternative economic forms, especially those that are more socially and ecologically just. This paper makes an argument for putting sustainable development through the same theoretical scrutiny. Drawing on examples from the US we recruit the concept of “actually existing sustainabilities” from Altvater’s concept “actually existing socialisms” as an entry point to this conversation. Our purpose is to show that the potential for sustainability in the US exists in current local policies and practices if we rethink how we frame it.     

Rate of strike-slip motion on the Amanos Fault (Karasu Valley, southern Turkey) constrained by K–Ar dating and geochemical analysis of Quaternary basalts

The left-lateral Amanos Fault follows a 200-km-long and up to 2-km-high escarpment that bounds the eastern margin of the Amanos mountain range and the western margin of the Karasu Valley in southern Turkey, just east of the northeastern corner of the Mediterranean Sea. Regional kinematic models have reached diverse conclusions as to the role of this fault in accommodating relative motion between either the African and Arabian, Turkish and African, or Turkish and Arabian plates. Local studies have tried to estimate its slip rate by K–Ar dating Quaternary basalts that erupted within the Amanos Mountains, flowed across it into the Karasu Valley, and have since become offset. However, these studies have yielded a wide range of results, ranging from 0.3 to 15 mm a⁻¹, which do not allow the overall role and significance of this fault in accommodating crustal deformation to be determined. We have used the Cassignol K–Ar method to date nine Quaternary basalt samples from the vicinity of the southern part of the Amanos Fault. These basalts exhibit a diverse chemistry, which we interpret as a consequence varying degrees of partial melting of their source combined with variable crustal contamination. This dating allows us to constrain the Quaternary slip rate on the Amanos fault to 1.0 to 1.6 mm a⁻¹. The dramatic discrepancies between past estimates of this slip rate are partly due to technical difficulties in K–Ar dating of young basalts by isotope dilution. In addition, previous studies at the key locality of Hacılar have unwittingly dated different, chemically distinct, flow units of different ages that are juxtaposed. This low slip rate indicates that, at present, the Amanos Fault takes up a small proportion of the relative motion between the African and Arabian plates, which is transferred southward to the Dead Sea Fault Zone. It also provides strong evidence against the long-standing view that its slip continues offshore to the southwest along a hypothetical left-lateral fault zone located south of Cyprus.     

Improved age constraint for pre‐ and post‐Anglian temperate‐stage deposits in north Norfolk,UK, from analysis of serine decomposition in Bithynia opercula

The ‘new glacial stratigraphy’ (NGS) of Britain postulates that deposits hitherto assigned to the Anglian glaciation in Marine Isotope Stage (MIS) 12 represent MIS 16, 12, 10 and 6. This controversial idea can be tested at Sidestrand in north Norfolk, where fossiliferous temperate‐stage deposits underlie the oldest and overlie the youngest of the glacial deposits. Previous work has considered biostratigraphy and amino acid dating of these temperate‐stage deposits, but did not achieve tight age constraint using the amino acid evidence alone. The total hydrolysable amino acid fraction in intra‐crystalline protein from Bithynia tentaculata opercula has previously been analysed for concentrations of serine and alanine. Statistical screening of these data gives alanine/serine ratios of 4.572 ± 0.114 for the Sidestrand Hall Member (beneath the glacial deposits) and 3.564 ± 0.091 for the Sidestrand Cliff Formation (overlying the glacial deposits). These ratios imply ages of MIS 13a and 11c, respectively, indicating the latest Cromerian and early Hoxnian interglacials and invalidating the NGS. Copyright © 2009 John Wiley & Sons, Ltd.