Marta J. K. Flohr

Alkaline igneous rocks of Magnet Cove, Arkansas: Mineralogy and geochemistry of syenites

Abstract Syenites from the Magnet Cove alkaline igneous complex form a diverse mineralogical and geochemical suite. Compositional zoning in primary and late-stage minerals indicates complex, multi-stage crystallization and replacement histories. Residual magmatic fluids, rich in F, Cl, CO 2 and H 2 O, reacted with primary minerals to form complex intergrowths of minerals such as rinkite, fluorite, V-bearing magnetite, F-bearing garnet and aegirine. Abundant sodalite and natrolite formed in pegmatitic segregations within nepheline syenite where Cl- and Na-rich fluids were trapped. During autometasomatism compatible elements such as Mn, Ti, V and Zr were redistributed on a local scale and concentrated in late-stage minerals. Early crystallization of apatite and perovskite controlled the compatible behavior of P and Ti, respectively. The formation of melanite garnet also affected the behaviour of Ti, as well as Zr, Hf and the heavy rare-earth elements. Pseudoleucite syenite and garnet-nepheline syenite differentiated along separate trends, but the two groups are related to the same parental magma by early fractionation of leucite, the presumed precursor of intergrowths of K-feldspar and nepheline. The Diamond Jo nepheline syenite group defines a different differentiation trend. Sphene-nepheline syenite, alkali syenite and several miscellaneous nepheline syenites do not consistently plot with the other syenite groups or each other on element and oxide variation diagrams, indicating that they were derived from still other parental syenite magmas. Mineral assemblages indicate that relatively high ƒ; O2 , at or above the fayalite-magnetite-quartz buffer, prevailed throughout the crystallization history of the syenites.

Chemical fluxes and origin of a manganese carbonate-oxide-silicate deposit in bedded chert

Abstract Lens-like rhodochrosite-rich bodies within interbedded chert and shale are associated with basalt and/or graywacke in ophiolitic and orogenic zones. The Buckeye manganese mine in the Franciscan Complex of the California Coast Ranges is associated with metagraywacke. Despite blueschist-facies metamorphism, this deposit preserves the compositions and some textural features of its sedimentary protoliths. For this reason, it is a suitable deposit with which to compare more intensely altered deposits, or deposits originating in different paleoenvironments. Six Mn-rich and three Mn-poor minerals form monomineralic layers and mixtures: rhodochrosite, gageite, Mn-oxides (hausmannite, braunite), divalent Mn-silicates (caryopilite, taneyamalite), chlorite, quartz (metachert) and aegirine-augite. The Mn-rich protoliths have high Mn/Fe combined with relatively low concentrations of Ca, Al, Ti, Co, Ni, Cu, Th and REE. REE patterns of various protoliths are distinct. Rhodochrosite and gageite layers are depleted (seawater × 5 · 104) and flat, whereas patterns of metachert and the Mn-silicate-rich layers mimic the patterns of metashale and metagraywacke (seawater × 106). Hausmannite layers have flat patterns (seawater × 7 · 104) whereas braunite-rich layers are more enriched (seawater × 2 · 105) and show a distinct positive Ce anomaly. Factor analysis reveals components and fluxes attributed to sub-seafloor fluids (Ni, As, Zn, Sb, W, Mn), seawater (Mg, Au, V, Mo), detritus and veins (Ca, Ba, Sr). Silica is negatively correlated with the sub-seafloor factor. The observed variances indicate that water from the sediment column mixed with seawater, that deposition occurred near the sediment-seawater interface before mixtures of subsurface fluid and seawater homogenized, and that the system was not entirely closed during metamorphism. The variations in REE enrichment can be related to kinetics of deposition: rhodochrosite and gageite were precipitated most rapidly, and therefore were the protoliths that most effectively diluted the REE-rich background resulting from fine clastic material (derived from distal turbidites). The variation of the Ce anomaly and U/Th among diverse lithologies and the differences in Mn oxidation states are consistent with progressive dilution of reduced subsurface fluids with oxidized seawater. By this scheme, rhodochrosite, gageite and hausmannite were deposited from the most reduced fluids, braunite from intermediate mixtures, and Mn-silicates from the sub-seafloor fluids most diluted with fresh seawater. Comparison of the Buckeye with other lens-like and sheet-like deposits having high Mn/Fe and containing Mn3+ and/or Mn2+ suggests that each had three essential fluxes: a sub-seafloor source of Mn, a local source of very soluble silica and a source of relatively fresh, oxygenated water. Additional fluxes, such as clastics, appear to be more characteristic of the paleoenvironment than the three essential fluxes.

Mineralogy and geochemistry of two metamorphosed sedimentary manganese deposits, Sierra Nevada, California, USA

Abstract Laminated to massive rhodochrosite, hausmannite, and Mn-silicates from the Smith prospect and Manga-Chrome mine, Sierra Nevada, California were deposited as ocean floor sediments associated with chert and shale. The principal lithologies at Smith are chert, argillite, rhodochrosite-, hausmannite- and chlorite-rich layers, and relatively uncommon layers of jacobsite. The Manga-Chrome mine also contains layers rich in manganoan calcite and caryopilite. Tephroite, rhodonite, spessartine, and accessory alleghanyite and sonolite formed during metamorphism. Volcaniclastic components are present at Manga-Chrome as metavolcanic clasts and as Mn-poor, red, garnet- and hematite-rich layers. There is no evidence, such as relict lithologies, that Mn was introduced into Mn-poor lithologies such as chert, limestone or mudstone. Replacement of Mn-poor phases by Mn-rich phases is observed only in the groundmass of volcanic clasts that appear to have fallen into soft Mn-rich mud. Manganiferous samples from the Smith prospect and Manga-Chrome mine have high Mn Fe and low concentrations of Ni, Cu, Zn, Co, U, Th and the rare-earth elements that are similar to concentrations reported from other ancient Mn deposits found in chert-greenstone complexes and from manganiferous sediments and crusts that are forming near modern sea floor vents. The Sierra Nevada deposits formed as precipitates of Mn-rich sediments on the sea floor, probably from mixtures of circulating hydrothermal fluids and seawater. The composition of a metabasalt from the Smith prospect is consistent with those of island-arc tholeiites. Metavolcanic clasts from the Manga-Chrome mine are compositionally distinct from the Smith metabasalt and have alkaline to calc-alkaline affinities. A back-arc basin is considered to be the most likely paleoenvironment for the formation of the Mn-rich lenses at the Manga-Chrome mine and, by association, the Smith prospect. Layers of rhodochrosite, hausmannite and chert preserve the composition and some textures of the sedimentary protoliths at both Sierra Nevada deposits. Jacobsite-rich layers probably represent a Fe-rich protolith. Caryopilite and manganoan calcite represent additional protoliths at the Manga-Chrome mine. The metamorphic assemblage prehnite-chlorite-epidote-calcite in a metabasalt from the Smith prospect constrains regional metamorphic conditions to a maximum temperature of 325°C and a pressure of 2 kbar. Slightly higher temperatures are indicated by the presence of actinolite in another metabasalt. Compositions of Mn-rich minerals in Smith samples are consistent with these metamorphic conditions.