Deposition of deep-sea manganese nodules

Manganese at equilibrium in seawater occurs dominantly as Mn²⁺ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O₂ and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 10⁸ ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn²⁺ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)₃⁰ and Fe(OH)₄^?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)₃.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.     

Assimilation and crystal accumulation in a mid-crustal magma chamber: the Sausfjellet pluton, north-central Norway

The Sausfjellet pluton is made up of two intrusive units emplaced into high-grade metamorphic rocks of the Helgeland Nappe Complex of the Uppermost Allochthon in the Norwegian Caledonides. The eastern part of the pluton intruded marble and less voluminous calc-silicate and pelitic rocks. The western half is hosted predominantly by semi-pelitic migmatite with intercalated marble. Remelting of the migmatite during pluton emplacement occurred in a thermal aureole as much as 1000 m wide. The early gabbroic unit forms the southeastern part of the body; it consists of hornblende-bearing to hornblende-rich gabbro and diorite which is thought to have crystallized from an H₂O-rich andesitic parental magma. The younger dioritic unit underlies the central and western parts of the pluton, as well as a zone as much as 200 m wide that separates the rest of the pluton from its host rocks (herein the “annular zone”). The interior or central zone of the dioritic unit is pyroxene diorite that is locally interlayered with anorthosite. The western and annular zones are, by comparison, mineralogically heterogeneous. They range from diorite to quartz monzonite and from biotite-bearing two- and three-pyroxene assemblages to biotite–hornblende assemblages. Neither rock type nor mafic assemblage is correlated with position in the pluton or proximity to a contact. Stoped blocks of a distinctive coarse-grained diorite, as well as pyroxene-rich calc-silicates, are present in the gabbroic unit and the central zone of the dioritic unit. The few stoped blocks observed in the western zone of the dioritic unit are predominantly quartz-rich gneiss. Chemical variation in the central zone of the dioritic unit is interpreted to result from accumulation of pyroxenes+plagioclase from an H₂O-poor andesitic parent. These rocks have approximately constant δ¹⁸O of +6.6±0.2‰ and lack evidence of in situ assimilation. Heterogeneities in the western and annular zones of the dioritic unit are reflected in variable, anomalously enriched incompatible element contents and in δ¹⁸O, which ranges from +6.7‰ to +8.6‰. Petrologic models indicate that the magma parental to the central zone could also be parental to the western and annular zones. If so, evolution of the western and annular zone magma was by crystal accumulation and assimilation of metapelitic host rocks. As much as 20% of the mass of the western and annular zones can be ascribed to assimilated material, which apparently entered the magma by stoping. Therefore, the asymmetrical zoning of the pluton is due to differences in host rock compositions and the relative ability of the magma to assimilate its host rocks.     

Volatiles,vesicles, and vugs: Unraveling the magmatic and eruptive histories of Steno crater basalts

In 1972, Apollo 17 astronauts returned 170.4 kg of lunar material. Within 1 month of their return, a subset of those samples was specially curated with the forethought that future analytical techniques would offer new insight into the formation and evolution of the Moon. Of interest in this work is sample 71036, a basalt collected from the rim of Steno crater in the Taurus–Littrow Valley, which was stored frozen and was processed and released for study 50 years later. We report, for the first time, the detailed mineralogy and petrology of 71036 and its companion samples 71035, 71037, and 71055 using a novel combination of 2-D and 3-D methods. We investigate lunar volatiles through in situ measurements of apatite and 3-D measurements of vesicles to understand the degassing histories of the Steno crater basalts. Our coupled 2-D petrography and 3-D tomography data sets support a model of the Steno crater basalts crystallizing in the upper crust of a mare lava flow. Apatite F and OH chemistry and the late-stage deformation of voids and formation of smaller vesicles provide evidence supporting coeval degassing of volatiles and crystallization of mesostasis apatite in Apollo 17 basalts. This work helps to close knowledge gaps surrounding the origin, magmatic evolution, emplacement, and crystallization history of high-titanium basalts.