Thermodynamic stability of CoOOH and its coprecipitation with manganese

A precipitate of cobalt oxyhydroxides formed by bubbling oxygen through a dilute solution of Co(NO₃)₂ held at pH 9.0 and 25°C was aged for 23 months in contact with the original solution, with access to atmospheric oxygen. Co₃O₄ and CoOOH were identified in the precipitate by X-ray diffraction. Chemical equilibria involving these solids were evaluated by measurements of solution pH and Co²⁺ activities and by redox potential measurements and gave a $\text{ΔG}{}_{\mathrm{coOOH}}{}^0$ of $\text{?92.3 ± 0.5 kcal/mole}$. This value and other thermodynamic data show relative feasibility of hypothetical reaction steps and changes in reaction paths during automated coprecipitation titrations and subsequent aging of a precipitate that finally contained βMnOOH, MnO₂ (birnessite) and CoOOH.     

Nonequilibrium models for predicting forms of precipitated manganese oxides

Manganese oxides precipitated by bubbling air through 0.01 molar solutions of MnCl₂, Mn(NO₃)₂, MnSO₄, or Mn(ClO₄)₂ at a constantly maintained pH of 8.5 to 9.5 at temperatures of 25°C or higher consisted mainly of hausmannite, Mn₃O₄. At temperatures near 0°C, but with other conditions the same, the product is feitknechtite, βMnOOH, except that if the initial solution is MnSO₄ and the temperature is near 0°C the product is a mixture of manganite, γMnOOH and groutite, αMnOOH.All these oxides are metastable in aerated solution and alter by irreversible processes to more highly oxidized species during aging. A two-step nonequilibrium thermodynamic model predicts that the least stable species, βMnOOH, should be most readily converted to MnO₂. Some preparations of βMnOOH aged in their native solution at 5°C attained a manganese oxidation state of +3.3 or more after 7 months. Hausmannite aged at 25°C altered to γMnOOH. The latter is more stable than a or βMnOOH, and manganese oxidation states above 3.0 were not reached in hausmannite precipitates during 4 months of aging. Initial precipitation of MnCO₃ rather than a form of oxide is likely only where oxygen availability is very low.Composition of solutions and oxidation state and morphology of solids were determined during the aging process by chemical analyses, X-ray and electron diffraction and transmission electron micrographs.     

Evolution of a Holocene banner bank controlled by morphodynamics and structural setting of a macrotidal coast: Saint-Brieuc Bay(NW-Europe)

The morphology and internal structure of the Horaine Bank(Bay of Saint-Brieuc, NW France) are described based on multibeam echosounder and high-resolution seismic datasets coupled with vibro-core data. The Horaine Bank shows large-scale bedforms in the lee of a submerged rocky shoal, which allowed defining it as a Banner Bank.The internal structure of the sandbank reveals four seismic units(U1–U4) on a Cambrian basement(U0). The basal unit U1 is interpreted as reworked lowstand fluvial sediments those infilled micro incised valleys during a rise in sea level. This unit is overlain by paleo-coastal barrier sand-spit(U2) whose development was controlled by swell in the context of a rapid rise in sea level. The successive prograding unit(U3) is interpreted as flooding deposits in continuity with unit U2. The unit U4 is characterized by oblique reflectors oriented in two opposite directions. This last unit, dated post 3500 yr BP, corresponds to migrating dunes superimposed on the bank and observable in the high-resolution bathymetric data. The strong correlation between tidal currents and the apparent clockwise migration of dune crests suggests the presence of a tidal gyre controlling the present-day dynamics of most of the Horaine bank dunes. This study proposes a new model for the construction of banner banks characterized by the gradual transition of a sand spit to a banner bank during marine transgression and ensuing hydrodynamic variability.     

Genetic techniques for livestock breeding: Restructuring institutional relationships in agriculture

This paper explores some of the key institutional transformations in livestock breeding associated with the increasing significance of genetic techniques, situating this within an assessment of an emerging agricultural bioeconomy. Focusing on beef cattle and sheep breeding in the United Kingdom, the paper examines how a move towards the involvement of international and corporate interests in livestock breeding is restructuring the network of institutional interests affecting the knowledge and decision making of individual breeders. The paper suggests that the structural transformation of beef cattle and sheep breeding is complicated by the need for negotiation between breeders’ ‘traditional’ knowledge-practices and the ‘geneticised’ techniques being made available to them. We are thus seeing the emergence of new and complex interactions between the major actors which are reconfiguring power relationships in the UK livestock breeding sector.