L. Gordon Medaris

Experimental studies of the distribution of rare earths as trace elements among silicate minerals and liquids and water

Abstract The distribution of the REE between synthetic diopside, forsterite, enstatite, and gaseous water and between natural plagioclase, 2 rhyolite obsidian melts and gaseous water have been measured. Values for distribution coefficients ( D ) for the REE between the minerals and aqueous fluid vary significantly over the temperature range of 550°C to 850°C, but little variation was found for the values of D between the silicate liquids and aqueous fluid over a temperature range of 100°C. By assuming that the values of D for the silicate liquids are independent of major element composition and temperature, it is possible to calculate values of D for REE between silicate minerals and silicate liquid. The values obtained for diopside, forsterite, enstatite and plagioclase compare favorably with those obtained for the natural materials clinopyroxene, olivine, orthopyroxene and plagioclase (except for Eu). The values of D for diopside were found to increase and those for forsterite and enstatite to decrease with increasing temperatuie. Values of temperature of equilibration for natural minerals obtained by extrapolation of graphs for experimental data of In D against 1/ T for the systems diopside-silicate liquid, forsterite-silicate liquid, and forsterite-diopside fall within a reasonable range, suggesting the possibility of geothermometry using REE concentrations of minerals.

Differentiating pedogenesis from diagenesis in early terrestrial paleoweathering surfaces formed on granitic composition parent materials

Unconformable surfaces separating Precambrian crystalline basement and overlying Proterozoic to Cambrian sedimentary rocks provide an exceptional opportunity to examine the role of primitive soil ecosystems in weathering and resultant formation of saprolite (weathered rock retaining rock structure) and regolith (weathered rock without rock structure), but many appear to have been affected by burial diagenesis and hydrothermal fluid flow, leading some researchers to discount their suitability for such studies. We examine one modern weathering profile (Cecil series), four Cambrian paleoweathering profiles from the North American craton (Squaw Creek, Franklin Mountains, Core SQ‐8, and Core 4), one Neoproterozoic profile (Sheigra), and one late Paleoproterozoic profile (Baraboo), to test the hypothesis that these paleoweathering profiles do provide evidence of primitive terrestrial weathering despite their diagenetic and hydrothermal overprinting, especially additions of potassium. We employ an integrated approach using (1) detailed thin‐section investigations to identify characteristic pedogenic features associated with saprolitization and formation of well‐drained regoliths, (2) electron microprobe analysis to identify specific weathered and new mineral phases, and (3) geochemical mass balance techniques to characterize volume changes during weathering and elemental gains and losses of major and minor elements relative to the inferred parent materials. There is strong pedogenic evidence of paleoweathering, such as clay illuviation, sepic‐plasmic fabrics, redoximorphic features, and dissolution and alteration of feldspars and mafic minerals to kaolinite, gibbsite, and Fe oxides, as well as geochemical evidence, such as whole‐rock losses of Na, Ca, Mg, Si, Sr, Fe, and Mn greater than in modern profiles. Evidence of diagenesis includes net additions of K, Ba, and Rb determined through geochemical mass balance, K‐feldspar overgrowths in overlying sandstone sections, and K‐feldspars with reaction rims in weathered basement. The sub‐Cambrian paleoweathering profiles formed on granite are remarkably similar to modern weathering profiles formed on granite, in spite of overprinting by potassium diagenesis.

Gadolinium: Distribution between Aqueous and Silicate Phases.

Studies of the partition of trivalent gadolinium between aqueous and silicate phases have been made at temperatures from 800� to 900�C and at pressures from 500 to 1000 bars. Constant values for the distribution coefficients for forsterite, enstatite, and diopside were obtained over a concentration range from 0.6 part per billion to 4 parts per thousand in the solid phases. Ratios of silicate crystal-aqueous phase distribution coefficients to silicate melt-aqueous phase distribution coefficients are close to the values for silicate crystal-silicate melt distribution coefficients estimated from natural systems. The free ion activity of trivalent gadolinium in the silicate melts appears to be less than one-hundredth of its value for aqueous phases of the same concentration.

Orphan Arctic Ocean metasediment clasts: Local derivation from Alpha Ridge or pre-2.6 Ma ice rafting?

Phyllonite and metaquartzite clasts occur in early Pliocene or possibly Miocene sediment at the base of the University of Wisconsin Arctic Ocean core Fl-380. Single-crystal 40 Ar/ 39 Ar laserprobe ages derived from feldspars in sediment enclosing the clasts range from Middle and Late Proterozoic to Paleozoic. The clasts occur in sediment deposited 1–2 m.y. earlier than any previously reported central Arctic Ocean ice-rafted debris, and although an ice-rafted origin may be possible, a local source such as adjacent Alpha Ridge bedrock should also be considered.

Axial‐type olivine crystallographic preferred orientations: The effect of strain geometry on mantle texture

The effect of finite strain geometry on crystallographic preferred orientation (CPO) is poorly constrained in the upper mantle. Specifically, the relationship between shape preferred orientation (SPO) and CPO in the mantle rocks remains unclear. We analyzed a suite of 40 spinel peridotite xenoliths from Marie Byrd Land, west Antarctica. X-ray computed tomography allows for quantification of spinel SPO, which ranges from prolate to oblate shape. Electron backscatter diffraction analysis reveals a range of olivine CPO patterns, including A-type, axial-[010], axial-[100], and B-type patterns. Until now, these CPO types were associated with different deformation conditions, deformation mechanisms, or strain magnitudes. Microstructures and deformation mechanism maps suggest that deformation in all studied xenoliths is dominated by dislocation-accommodated grain boundary sliding. For the range of temperatures (779–1198 oC), extraction depths (39–72 km), differential stresses (2–60 MPa), and water content (up to 500 H/106Si) of the xenolith suite, variations in olivine CPO do not correlate with changes in deformation conditions. Here we establish for the first time in naturally deformed mantle rocks that finite strain geometry controls the development of axial-type olivine CPOs; axial-[010] and axial-[100] CPOs form in relation to oblate and prolate fabric ellipsoids, respectively. Girdling of olivine crystal axes results from intracrystalline slip with activation of multiple slip systems, and grain boundary sliding. Our results demonstrate that mantle deformation may deviate from simple shear. Olivine texture in field studies and seismic anisotropy in geophysical investigations can provide critical constraints for the 3D strain in the upper mantle.

Anatomy of a Sub-Cambrian Paleosol in Wisconsin: Mass Fluxes of Chemical Weathering and Climatic Conditions in North America during Formation of the Cambrian Great Unconformity

A paleosol beneath the Upper Cambrian Mount Simon Sandstone in Wisconsin provides an opportunity to evaluate the characteristics of Cambrian weathering in a subtropical climate, having been located at 20°S paleolatitude 500 My ago. The 285-cm-thick paleosol resulted from advanced chemical weathering of a gabbroic protolith, recording a total mass loss of 50%. Weathering of hornblende and plagioclase produced a pedogenic assemblage of quartz, chlorite, kaolinite, goethite, and, in the lowest part of the profile, siderite. Despite the paucity of quartz in the protolith and 40% removal of SiO2 from the profile, quartz constitutes 11%–23% of the pedogenic mineral assemblage. Like many other Precambrian and Cambrian paleosols in the Lake Superior region, the paleosol experienced potassium metasomatism, now containing 10%–25% mixed-layer illite-vermiculite and 5%–44% potassium feldspar. Estimates of mean annual precipitation and mean annual temperature are 1777 mm y−1 and 20.1°C, respectively, which are consistent with a paleolatitude of 20°S. For an atmospheric CO2 concentration of 4000–6000 ppm at 550–500 Ma, the duration of weathering is constrained to have been between 20,000 and 100,000 y. When the effects of erosion and influence of protolith composition are considered, the degree, or maturity, of weathering for the Wisconsin paleosol and four other sub-Cambrian paleosols is comparable to that for two modern soils in subtropical and temperate climates, despite the lack of land plants in Cambrian time. Such correspondent degrees of weathering likely result from the effects of elevated levels of atmospheric CO2 and microbial activity on weathering in Cambrian time.