Geology topics

Andrea Koschinsky

Publications and source records attributed to Andrea Koschinsky.

7 recordsLinked to original sources

USGS2022

Crystal chemistry of thallium in marine ferromanganese deposits

Our understanding of the up to 7 orders of magnitude partitioning of thallium (Tl) between seawater and ferromanganese (FeMn) deposits rests upon two foundations: (1) being able to quantify the Tl(I)/Tl(III) ratio that reflects the extent of the oxidative scavenging of Tl by vernadite (δ-MnO 2 ), the principle manganate mineral in oxic and suboxic environments, and (2) being able to determine the sorption sites and bonding environments of the Tl(I) and Tl(III) complexes on vernadite. We investigated these foundations by determining the oxidation state and chemical form of Tl in FeMn crusts and nodules from the global oceans at a Tl concentration ranging from several hundred ppm (mg/kg) down to the low ppm level. Seventeen hydrogenetic crusts and eleven nodules from the Pacific, Atlantic, Arctic, and Indian Oceans and Baltic Sea were characterized by chemical analysis, X-ray diffraction, Raman spectroscopy, Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, Tl L 3 -edge high energy-resolution XANES (HR-XANES) spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The Tl concentration increases linearly from 1.5 to 319 ppm with the Mn/Fe ratio in Fe-vernadite from hydrogenetic crusts, whereas the percentage of Tl(III) to total Tl varies between 62 and 100% independent of both the Mn/Fe and Mn(III)/Mn(IV) ratios. The data, complemented by molecular modeling of the Tl(III) coordination and by XANES calculations, suggest that the enrichment of Tl in Fe-vernadite is driven by (1) the oxidative uptake of octahedrally coordinated Tl(III) above the vacant Mn(IV) sites and on the layer edges of the vernadite layers, and (2) the sorption of Tl(I) on the crystallographic site of Ba at the surface of the vernadite layers, which is an analogue to the surface site of K. Thus, Tl has a high affinity for vernadite regardless of its oxidation state, and the lack of correlation between Tl(III) and the Mn/Fe ratio in FeMn crusts is explained by the affinity of Tl(I) for the Ba site. The Tl concentration varies between 2 and 112 ppm in surface and buried nodules independent of the Mn/Fe ratio, and the percentage of Tl(III) varies between 0 and 100%. Nodules subjected to sediment diagenesis with replacement of layered vernadite by tunneled todorokite are depleted in Tl and have more reduced thallium. Knowledge of the complex interplay of mineralogy, surface chemical processes, and crystallographic siting is required to understand the variability of Tl concentrations, redox state, and acquisition processes by marine FeMn deposits.

ACS Earth and Space Chemistry↗

USGS2020

The effects of phosphatization on the mineral associations and speciation of Pb in ferromanganese crusts

The older layers of thick ferromanganese (FeMn) crusts from the central Pacific Ocean have undergone diagenetic phosphatization, during which carbonate fluorapatite (CFA) filled fractures and pore space and replaced carbonates. The effects of phosphatization on individual trace metal concentrations, speciation, and phase associations in FeMn crusts remain poorly understood yet may be important to metal enrichment mechanisms, paleoceanography, and extractive metallurgy. This study examines the concentrations, speciation, and mineral phase associations of Pb in phosphatized and nonphosphatized layers within three Pacific Ocean crusts using standard chemical and mineralogical techniques, in addition to bulk X-ray absorption spectroscopy (XAS) and microfocused X-ray fluorescence (μ-XRF) mapping. Our findings challenge the conclusions of previous works, which reported that most Pb in phosphatized crusts was associated with the CFA-dominated residual phase after sequential leaching experiments. These results were interpreted as an indication of Pb transfer from the oxide phases to diagenetic CFA during phosphatization. However, our results reveal an inverse correlation of Pb with Ca and P in the μ-XRF mapping of in situ FeMn crust sections and bulk chemistry. Furthermore, XAS measurements reveal that Pb speciation in bulk phosphatized FeMn crust layers is very similar to nonphosphatized layers, indicating only minor, if any, change in speciation during diagenetic phosphatization. Small differences in the EXAFS spectra for one highly phosphatized layer indicate that minor amounts of Pb may have been altered during phosphatization, but the new Pb-bearing phase was not unequivocally identified. Taken together, our results demonstrate that Pb speciation is not significantly affected by phosphatization.

Earth and Space Chemistry↗

USGS2017

Marine ferromanganese encrustations: Archives of changing oceans

Marine iron–manganese oxide coatings occur in many shallow and deep-water areas of the global ocean and can form in three ways: 1) Fe–Mn crusts can precipitate from seawater onto rocks on seamounts; 2) Fe–Mn nodules can form on the sediment surface around a nucleus by diagenetic processes in sediment pore water; 3) encrustations can precipitate from hydrothermal fluids. These oxide coatings have been growing for thousands to tens of millions of years. They represent a vast archive of how oceans have changed, including variations of climate, ocean currents, geological activity, erosion processes on land, and even anthropogenic impact. A growing toolbox of age-dating methods and element and isotopic signatures are being used to exploit these archives.

Elements↗

USGS2016

Marine phosphorites as potential resources for heavy rare earth elements and yttrium

Marine phosphorites are known to concentrate rare earth elements and yttrium (REY) during early diagenetic formation. Much of the REY data available are decades old and incomplete, and there has not been a systematic study of REY distributions in marine phosphorite deposits that formed over a range of oceanic environments. Consequently, we initiated this study to determine if marine phosphorite deposits found in the global ocean host REY concentrations of high enough grade to be of economic interest. This paper addresses continental-margin (CM) and open-ocean seamount phosphorites. All 75 samples analyzed are composed predominantly of carbonate fluorapatite and minor detrital and authigenic minerals. CM phosphorites have low total REY contents (mean 161 ppm) and high heavy REY (HREY) complements (mean 49%), while seamount phosphorites have 4–6 times higher individual REY contents (except for Ce, which is subequal; mean ΣREY 727 ppm), and very high HREY complements (mean 60%). The predominant causes of higher concentrations and larger HREY complements in seamount phosphorites compared to CM phosphorites are age, changes in seawater REY concentrations over time, water depth of formation, changes in pH and complexing ligands, and differences in organic carbon content in the depositional environments. Potential ore deposits with high HREY complements, like the marine phosphorites analyzed here, could help supply the HREY needed for high-tech and green-tech applications without creating an oversupply of the LREY.

Minerals↗

USGS2014

Deep-ocean ferromanganese crusts and nodules

Ferromanganese crusts and nodules may provide a future resource for a large variety of metals, including many that are essential for emerging high- and green-technology applications. A brief review of nodules and crusts provides a setting for a discussion on the latest (past 10 years) research related to the geochemistry of sequestration of metals from seawater. Special attention is given to cobalt, nickel, titanium, rare earth elements and yttrium, bismuth, platinum, tungsten, tantalum, hafnium, tellurium, molybdenum, niobium, zirconium, and lithium. Sequestration from seawater by sorption, surface oxidation, substitution, and precipitation of discrete phases is discussed. Mechanisms of metal enrichment reflect modes of formation of the crusts and nodules, such as hydrogenetic (from seawater), diagenetic (from porewaters), and mixed diagenetic–hydrogenetic processes.

Book chapter↗

USGS1999

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↗

USGS1996

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↗