Transmission electron microscopy of subsolidus oxidation and weathering of olivine

Olivine crystals in basaltic andesites which crop out in the Abert Rim, south-central Oregon have been studied by high-resolution and analytical transmission electron microscopy. The observations reveal three distinct assemblages of alteration products that seem to correspond to three episodes of olivine oxidation. The olivine crystals contain rare, dense arrays of coherently intergrown Ti-free magnetite and inclusions of a phase inferred to be amorphous silica. We interpret this first assemblage to be the product of an early subsolidus oxidation event in the lava. The second olivine alteration assemblage contains complex ordered intergrowths on (001) of forsterite-rich olivine and laihunite (distorted olivine structure with Fe³⁺ charge balanced by vacancies). Based on experimental results for laihunite synthesis (Kondoh et al. 1985), these intergrowths probably formed by olivine oxidation between 400 and 800°C. The third episode of alteration involves the destruction of olivine by low-temperature hydrothermal alteration and weathering. Elongate etch-pits and channels in the margins of fresh olivine crystals contain semi-oriented bands of smectite. Olivine weathers to smectite and hematite, and subsequently to arrays of oriented hematite crystals. The textures resemble those reported by Eggleton (1984) and Smith et al. (1987). We find no evidence for a metastable phase intermediate between olivine and smectite (M — Eggleton 1984). The presence of laihunite exerts a strong control on the geometry of olivine weathering. Single laihunite layers and laihunite-forsteritic olivine intergrowths increase the resistance of crystals to weathering. Preferential development of channels between laihunite layers occurs where growth of laihunite produced compositional variations in olivine, rather than where coherency-strain is associated with laihunite-olivine interfaces.     

Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

Modelling weathering processes at the catchment scale: The WITCH numerical model

A numerical model of chemical weathering in soil horizons and underlying bedrock (WITCH) has been coupled to a numerical model of water and carbon cycles in forest ecosystems (ASPECTS) to simulate the concentration of major species within the soil horizons and the stream of the Strengbach granitic watershed, located in the Vosges Mountains (France). For the first time, simulations of solute concentrations in soil layers and in the catchment river have been performed on a seasonal basis. The model is able to reproduce the concentrations of most major species within the soil horizons, as well as catching the first-order seasonal fluctuations of aqueous calcium, magnesium and silica concentrations. However, the WITCH model underestimates concentrations of Mg²⁺ and silica at the spring of the catchment stream, and significantly underestimates Ca²⁺ concentration. The deficit in calculated calcium can be compensated for by dissolution of trace apatite disseminated in the bedrock. However, the resulting increased Ca²⁺ release yields important smectite precipitation in the deepest model layer (in contact with the bedrock) and subsequent removal of large amount of silica and magnesium from solution. In contrast, the model accurately accounts for the concentrations of major species (Ca, Mg and silica) measured in the catchment stream when precipitation of clay minerals is not allowed. The model underestimation of Mg²⁺ and H₄SiO₄ concentrations when precipitation of well crystallized smectites is allowed strongly suggests that precipitation of well crystallized clay minerals is overestimated and that more soluble poorly crystallized and amorphous materials may be forming. In agreement with observations on other watersheds draining granitic rocks, this study indicates that highly soluble trace calcic phases control the aqueous calcium budget in the Strengbach watershed.     

Genesis of monazite and Y zoning in garnet from the Black Hills, South Dakota

The paragenesis of monazite in metapelitic rocks from the contact aureole of the Harney Peak Granite, Black Hills, South Dakota, was investigated using zoning patterns of monazite and garnet, electron microprobe dating of monazite, bulk-rock compositions, and major phase mineral equilibria. The area is characterized by low-pressure and high-temperature metamorphism with metamorphic zones ranging from garnet to sillimanite zones. Garnet porphyroblasts containing euhedral Y annuli are observed from the garnet to sillimanite zones. Although major phase mineral equilibria predict resorption of garnet at the staurolite isograd and regrowth at the andalusite isograd, textural and mass balance analyses suggest that the formation of the Y annuli is not related to the resorption-and-regrowth of garnet having formed instead during garnet growth in the garnet zone. Monazite grains in Black Hills pelites were divided into two generations on the basis of zoning patterns of Y and U: monazite 1 with low-Y and -U and monazite 2 with high-Y and -U. Monazite 1 occurs in the garnet zone and persists into the sillimanite zone as cores shielded by monazite 2 which starts to form in the andalusite zone. Pelites containing garnet porphyroblasts with Y annuli and monazite 1 with patchy Th zoning are more calcic than those with garnet with no Y annuli and monazite with concentric Th zoning. Monazite 1 is attributed to breakdown of allanite in the garnet zone, additionally giving rise to the Y annuli observed in garnet. Monazite 2 grows in the andalusite zone, probably at the expense of garnet and monazite 1 in the andalusite and sillimanite zones. The ages of the two different generations of monazite are within the precision of chemical dating of electron microprobe. The electron microprobe ages of all monazites from the Black Hills show a single ca. 1713 Ma population, close to the intrusion age of the Harney Peak Granite (1715 Ma). This study demonstrates that Y zoning in garnet and monazite are critical to the interpretation of monazite petrogenesis and therefore monazite ages.     

New typologies for estuarine morphology

New theories to explain how tides and river flow determine estuarine bathymetries have been developed. The range of validity of these theories has been subsequently assessed against a recently available observational data set.Success in reproducing the evolution of estuarine bathymetries that has occurred over the last 10 000 years provides the basis for the translation, here, of these theories into new typologies. These then provide reference frameworks to enhance our perspective on existing morphologies and identify ‘anomalous’ estuaries. Further refinement of these new theories requires analyses of causal factors responsible for such anomalies drawing on classical morphological experience. These frameworks can also be used for calculating likely future bathymetric adjustments for prescribed changes in mean sea level, tidal amplitudes, river flow and sediment supply.     

Sources of Sediment in Lake Pepin on the Upper Mississippi River in Response to Holocene Climatic Changes

Sediments from Lake Pepin on the Mississippi River, southeastern Minnesota, are used as provenance tracers to assess variations in hydrology and sediment-transport during the middle Holocene. Three rivers contribute sediment to Lake Pepin, and each catchment is characterized by a distinctly different geologic terrain. The geochemical fingerprint for each drainage basin was determined from the elemental composition of heavy minerals in the silt-sized fraction of modern sediment samples. Down-core elemental abundances were compared with these fingerprints by use of a chemical-mass-balance model that apportions sediment to the source areas. We observed a decreased contribution from the Minnesota River during the interval ~6700–5500 ¹⁴C yr BP, which we attribute to decreased discharge of the Minnesota River, likely controlled by a combination of precipitation, snow melt, and groundwater input to the river. This hydrologic condition coincides with the mid-Holocene prairie period recorded by fossil pollen data. The occurrence of this feature in a proxy record for hydrologic variations supports the hypothesis that the mid-Holocene prairie period reflects drier conditions than before or after in midwestern North America.