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Geology topics

Michael Bau

Publications and source records attributed to Michael Bau.

4 recordsLinked to original sources

Normalized rare earth elements in water, sediments, and wine: identifying sources and environmental redox conditions

The concentrations of the rare earth elements (REE) in surface waters and sediments, when normalized on an element-by-element basis to one of several rock standards and plotted versus atomic number, yield curves that reveal their partitioning between different sediment fractions and the sources of those fractions, for example, between terrestrial-derived lithogenous debris and seawater-derived biogenous detritus and hydrogenous metal oxides. The REE of ancient sediments support their partitioning into these same fractions and further contribute to the identification of the redox geochemistry of the sea water in which the sediments accumulated. The normalized curves of the REE that have been examined in several South American wine varietals can be interpreted to reflect the lithology of the bedrock on which the vines may have been grown, suggesting limited fractionation during soil development.

American Journal of Analytical Chemistry

Mineral dissolution in the Cape Cod aquifer, Massachusetts, USA: I . Reaction stoichiometry and impact of accessory feldspar and glauconite on strontium isotopes, solute concentrations, and REY distribution

To compare relative reaction rates of mineral dissolution in a mineralogically simple groundwater aquifer, we studied the controls on solute concentrations, Sr isotopes, and rare earth element and yttrium (REY) systematics in the Cape Cod aquifer. This aquifer comprises mostly carbonate-free Pleistocene sediments that are about 90% quartz with minor K-feldspar, plagioclase, glauconite, and Fe-oxides. Silica concentrations and pH in the groundwater increase systematically with increasing depth, while Sr isotopic ratios decrease. No clear relationship between 87 Sr/ 86 Sr and Sr concentration is observed. At all depths, the 87 Sr/ 86 Sr ratio of the groundwater is considerably lower than the Sr isotopic ratio of the bulk sediment or its K-feldspar component, but similar to that of a plagioclase-rich accessory separate obtained from the sediment. The Si- 87 Sr/ 86 Sr-depth relationships are consistent with dissolution of accessory plagioclase. In addition, solutes such as Sr, Ca, and particularly K show concentration spikes superimposed on their respective general trends. The K-Sr- 87 Sr/ 86 Sr systematics suggests that accessory glauconite is another major solute source to Cape Cod groundwater. Although the authigenic glauconite in the Cape Cod sediment is rich in Rb, it is low in in-grown radiogenic 87 Sr because of its young Pleistocene age. The low 87 Sr/ 86 Sr ratios are consistent with equilibration of glauconite with seawater. The impact of glauconite is inferred to vary due to its variable abundance in the sediments. In the Cape Cod groundwater, the variation of REY concentrations with sampling depth resembles that of K and Rb, but differs from that of Ca and Sr. Shale-normalized REY patterns are light REY depleted, show negative Ce anomalies and super-chondritic Y/Ho ratios, but no Eu anomalies. REY input from feldspar, therefore, is insignificant compared to input from a K-Rb-bearing phase, inferred to be glauconite. These results emphasize that interpretation of groundwater chemistry, even in relatively simple aquifers, may be complicated by solute contributions from “exotic” accessory minerals such as glauconite. To detect such peculiarities, groundwater studies should combine the study of elemental concentration and isotopic composition of several solutes that show different geochemical behavior.

Massachusetts

Cobalt-rich ferromanganese crusts in the Pacific

Co-rich Fe-Mn crusts occur throughout the Pacific on seamounts, ridges, and plateaus where currents have kept the rocks swept clean of sediments at least intermittently for millions of years. Crusts precipitate out of cold ambient sea water onto hard-rock substrates forming pavements up to 250 mm thick. Crusts are important as a potential resource for Co, Ni, Pt, Mn, Tl, Te, and other metals, as well as for the paleoclimate signals stored in their stratigraphic layers. Crusts form at water depths of about 400 to 4000 m, with the thickest and most Co-rich crusts occurring at depths of about 800 to 2500 m, which may vary on a regional scale. Gravity processes, sediment cover, submerged and emergent reefs, and currents control the distribution and thickness of crusts on seamounts. Crusts occur on a variety of substrate rocks that generally decrease in the order, breccia, basalt, phosphorite, limestone, hyaloclastite, and mudstone. Because of this wide variety of substrate types, crusts are difficult to distinguish from the substrate using remotely sensed data, such as geophysical measurements, but are generally weaker and lighter-weight than the substrate. Crusts can be distinguished from the substrates, however, by their much higher gamma radiation levels. The mean dry bulk density of crusts is 1.3 g/cm3, the mean porosity is 60%, and the mean surface area is extremely high, 300 m2/g. Crusts generally grow at rates of 1 to 10 mm/Ma. Crust surfaces are botryoidal, which may be modified to a variety of forms by current erosion. In cross-section, crusts are generally layered, with individual layers displaying massive, botryoidal, laminated, columnar, or mottled textures. Characteristic layering is persistent regionally in the Pacific. Crusts are composed of ferruginous vernadite (δ-MnO2) and X-ray amorphous Fe oxyhydroxide, with moderate amounts of carbonate fluorapatite (CFA) in thick crusts and minor amounts of quartz and feldspar in most crusts. Elements most commonly associated with the vernadite phase include Mn, Co, Ni, Cd, and Mo, whereas those most commonly associated with Fe oxyhydroxide are Fe and As. Detrital phases are represented by Si, Al, K, Ti, Cr, Mg, Fe, and Na; the CFA phase by Ca, P, Sr, Y, and CO2; and a residual biogenic phase by Ba, Sr, Ce, Cu, V, Ca, and Mg. Crusts contain Co contents up to about 2.3%, Ni to 1%, and Pt to 3 ppm, with mean Fe/Mn ratios of 0.6 to 1.3. Fe/Mn decreases, whereas Co, Ni, Ti, and Pt increase in central Pacific crusts and Fe/Mn, Si, and Al increase in continental margin crusts and in crusts with proximity to west Pacific volcanic arcs. Vernadite and CFA-related elements decrease, whereas Fe, Cu, and detrital-related elements increase with increasing water depth of crust occurrence. Cobalt, Ce, Tl, and maybe also Ti, Pb, and Pt are strongly concentrated in crusts over other metals because of oxidation reactions. Total rare earth elements (REEs) commonly vary between 0.1% and 0.3% and are derived from sea water along with other hydrogenetic elements, Co, Mn, Ni, etc. Platinum, Rh, Ir, and some Ru in crusts are also derived from sea water, whereas Pd and the remainder of the Ru derive from detrital minerals. The older parts of thick crusts were phosphatized during at least two global phosphogenic events during the Tertiary, which mobilized and redistributed elements in those parts of the crusts. 240Silicon, Fe, Al, Th, Ti, Co, Mn, Pb, and U are commonly depleted, whereas Ni, Cu, Zn, Y, REEs, Sr, and Pt are commonly enriched in phosphatized layers compared to younger nonphosphatized layers. The dominant controls on the concentration of elements in crusts include the concentration of metals in sea water and their ratios, colloid surface charge, types of complexing agents, surface area, and growth rates. Crusts act as closed systems with regard to the isotopic ratios of Be, Nd, Pb, Hf, Os, and U-series, which in part have been used to date crusts and in part used as isotopic tracers of paleoceanographic and paleoclimatic conditions. Those tracers are especially useful in delineating temporal changes in deep-ocean circulation. Research and development on the technology of mining crusts are only in their infancy. Detailed maps of crust deposits and a better understanding of small-scale seamount topography are required to design the most appropriate mining equipment.

Book chapter

Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater

In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REY SN ) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for Y sn , and positive anomalies for La SN , Eu SN , Gd SN , and in most cases, Ce sn . They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REY SN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive Y sn anomalies, stronger positive La SN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to non-phosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, K d m , describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of K D Ce , which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce (IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower K D values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative “anomalies” occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in inorganic surface complex stability between Y and Ho and between Gd and its REE neighbours are similar to those shown by the stabilities of complexes with aminocarboxylic acids and are significantly larger than those shown by stabilities of complexes with carboxylic acids. Hence, sorption of Y and REEs onto hydrous Fe-Mn oxides may contribute significantly to the positive Y SN and Gd SN anomalies in seawater.

Geochimica et Cosmochimica Acta