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J.R. Hein

Publications and source records attributed to J.R. Hein.

At least 19 recordsLinked to original sources
USGS2013

Trace metal-rich Quaternary hydrothermal manganese oxide and barite deposit, Milos Island, Greece

The Cape Vani Mn oxide and barite deposit on Milos Island offers an excellent opportunity to study the three-dimensional characteristics of a shallow-water hydrothermal system. Milos Island is part of the active Aegean volcanic arc. A 1 km long basin located between two dacitic domes in northwest Milos is filled with a 35-50 m thick section of Quaternary volcaniclastic and pyroclastic rocks capped by reef limestone that were hydrothermally mineralized by Mn oxides and barite. Manganese occurs as thin layers, as cement of sandstone and as metasomatic replacement of the limestone, including abundant fossil shells. Manganese minerals include chiefly δ-MnO2, pyrolusite and ramsdellite. The MnO contents for single beds range up to 60%. The Mn oxide deposits are rich in Pb (to 3.4%), BaO (to 3.1%), Zn (to 0.8%), As (to 0.3%), Sb (to 0.2%) and Ag (to 10 ppm). Strontium isotopic compositions of the Mn oxide deposits and sulphur isotopic compositions of the associated barite show that the mineralizing fluids were predominantly sea water. The Mn oxide deposit formed in close geographical proximity to sulphide-sulphate-Au-Ag deposits and the two deposit types probably formed from the same hydrothermal system. Precipitation of Mn oxide took place at shallow burial depths and was promoted by the mixing of modified sea water (hydrothermal fluid) from which the sulphides precipitated at depth and sea water that penetrated along faults and fractures in the Cape Vani volcaniclastic and tuff deposits. The hydrothermal fluid was formed from predominantly sea water that was enriched in metals leached from the basement and overlying volcanogenic rocks. The hydrothermal fluids were driven by convection sustained by heat from cooling magma chambers. Barite was deposited throughout the time of Mn oxide mineralization, which occurred in at least two episodes. Manganese mineralization occurred by both focused and diffuse flow, the fluids mineralizing the beds of greatest porosity and filling dilatational fractures along with barite.

Milos Island↗
USGS2012

Copper-nickel-rich, amalgamated ferromanganese crust-nodule deposits from Shatsky Rise, NW Pacific

A unique set of ferromanganese crusts and nodules collected from Shatsky Rise (SR), NW Pacific, were analyzed for mineralogical and chemical compositions, and dated using Be isotopes and cobalt chronometry. The composition of these midlatitude, deep-water deposits is markedly different from northwest-equatorial Pacific (PCZ) crusts, where most studies have been conducted. Crusts and nodules on SR formed in close proximity and some nodule deposits were cemented and overgrown by crusts, forming amalgamated deposits. The deep-water SR crusts are high in Cu, Li, and Th and low in Co, Te, and Tl concentrations compared to PCZ crusts. Thorium concentrations (ppm) are especially striking with a high of 152 (mean 56), compared to PCZ crusts (mean 11). The deep-water SR crusts show a diagenetic chemical signal, but not a diagenetic mineralogy, which together constrain the redox conditions to early oxic diagenesis. Diagenetic input to crusts is rare, but unequivocal in these deep-water crusts. Copper, Ni, and Li are strongly enriched in SR deep-water deposits, but only in layers older than about 3.4 Ma. Diagenetic reactions in the sediment and dissolution of biogenic calcite in the water column are the likely sources of these metals. The highest concentrations of Li are in crust layers that formed near the calcite compensation depth. The onset of Ni, Cu, and Li enrichment in the middle Miocene and cessation at about 3.4 Ma were accompanied by changes in the deep-water environment, especially composition and flow rates of water masses, and location of the carbonate compensation depth.

Geochemistry, Geophysics, Geosystems↗
USGS2011

The molecular mechanism of Mo isotope fractionation during adsorption to birnessite

Fractionation of Mo isotopes during adsorption to manganese oxides is a primary control on the global ocean Mo isotope budget. Previous attempts to explain what drives the surprisingly large isotope effect δ97/95Modissolved-δ97/95Moadsorbed=1.8‰ have not successfully resolved the fractionation mechanism. New evidence from extended X-ray absorption fine structure analysis and density functional theory suggests that Mo forms a polymolybdate complex on the surfaces of experimental and natural samples. Mo in this polynuclear structure is in distorted octahedral coordination, while Mo remaining in solution is predominantly in tetrahedral coordination as MoO42- . Our results indicate that the difference in coordination environment between dissolved Mo and adsorbed Mo is the cause of isotope fractionation. The molecular mechanism of metal isotope fractionation in this system should enable us to explain and possibly predict metal isotope effects in other systems where transition metals adsorb to mineral surfaces.

Geochimica et Cosmochimica Acta↗
USGS2010

Constraints on the development of Proterozoic basins in central India from 40 Ar/ 39 Ar analysis of authigenic glauconitic minerals

Ages of some key stratigraphic sequences in central Indian Proterozoic basins are based predominantly on lithostratigraphic relationships that have been constrained by only a few radioisotopic dates. To help improve age constraints, single grains of glauconitic minerals taken from sandstone and limestone in two Proterozoic sequences in the Pranhita-Godavari Valley and the Chattisgarh basin were analyzed by the 40 Ar/ 39 Ar incremental heating method. Analysis of the age spectra distinguishes between ages that are interpreted to reflect the time of glauconite formation, and anomalous ages that result from inherited argon or postcrystallization heating. The analyses indicate an age of 1686 ± 6 Ma for the Pandikunta Limestone and 1566 ± 6 Ma for the Ramgundam Sandstone, two units in the western belt of Proterozoic sequences in Pranhita-Godavari Valley. Glauconite from the Chanda Limestone, in the upper part of this sequence, contains inherited 40 Ar but is interpreted to reflect an age of ca. 1200 Ma. Glauconite from the Somanpalli Group in the eastern belt of the Pranhita-Godavari Valley gives an age of 1620 ± 6 Ma. In the Chattisgarh basin, glauconite from two units gives disturbed ages that suggest a period of regional heating in the Chattisgarh basin at ca. 960–1000 Ma. These new ages indicate that these sequences are 200–400 m.y. older than previously recognized, which has important implications for geochemical studies of Mesoproterozoic ocean redox conditions in addition to providing important constraints on regional tectonics and lithostratigraphy.

GSA Bulletin↗
USGS2010

Variations in the fine-scale composition of a central Pacific ferromanganese crust: Paleoceanographic implications

A 47- to 60-mm-thick Fe-Mn crust from Horizon Guyot (water depth 1800–1780 m), central Pacific, was used to evaluate the potential of crusts as recorders of Neogene paleoceanographic and paleoclimatic conditions. The chemical composition was determined by microprobe for 16 elements from a polished thin section. Three analyses were made per millimeter and averaged to give the composition of each millimeter. The age of the crust was determined by measuring the strontium isotope composition of the crust and comparing it with the Tertiary seawater curve. The crust represents 18.5 m.y. of growth of Fe and Mn oxyhydroxides. The crust is composed of alternating botryoidal and laminated layers. The botryoidal layers formed during the same time intervals that widespread Neogene deep-sea hiatuses were forming in bottom sediments. The botryoidal layers represent growth during times of intensified deepwater flow, whereas the laminated intervals represent more quiescent conditions. The correspondence between the botryoidal layers and the Neogene hiatuses is so strong that we were able to choose a variable growth rate model over a constant growth rate model for the crust. Chemical changes in the crust take two forms. The first is represented by broad changes in the composition defined chiefly by fourth-order polynomial fits to the chemical profiles of each element with depth in the crust. The second is high-frequency changes in composition. The broader changes occurred primarily at about 15, 11.5, 7.4, 6.4, 5.2, and 4.6 Ma, which may correlate with major changes in paleoceanographic circulation and development of ice caps at the poles. The periods of the high-frequency changes may reflect climatic changes that resulted from orbital forcing. These high-frequency changes may correspond to the high-order eccentricity periods of 3.47, 2.04, and 1.31 m.y.

Paleoceanography and Paleoclimatology↗
USGS2010

Two major Cenozoic episodes of phosphogenesis recorded in equatorial Pacific seamount deposits

Seamount phosphorites have been recognized since the 1950s, but this is the first study to provide an in depth exploration of the origin and history of these widespread deposits. Representative samples from equatorial Pacific Cretaceous seamounts were analyzed for chemical, mineralogical, and stable isotope compositions. The phosphorites occur in a wide variety of forms, but most commonly carbonate fluorapatite (CFA) replaced middle Eocene and older carbonate sediment in a deep water environment (>1000 m). Element ratios distinguish seamount phosphorites from continental margin, plateau, and insular phosphorites. Uranium and thorium contents are low and total rare earth element (REE) contents are generally high. REE ratios and shale-normalized patterns demonstrate that the REEs and host CFA were derived from seawater. Strontium isotopic compositions compared with inferred Cenozoic seawater curves define two major episodes of Cenozoic phosphatization: Late Eocene/early Oligocene (39–34 Ma) and late Oligocene/early Miocene (27–21 Ma); three minor events are also indicated. The major episodes occurred at times of climate transition, the first from a nonglacial to glacial earth and the second from a predominantly glacial to warm earth. The paleoceanographic conditions that existed at those times initiated and sustained development of phosphorite by accumulation of dissolved phosphorus in the deep sea during relatively stable climatic conditions when oceanic circulation was sluggish. Fluctuations in climate, sealevel, and upwelling that accompanied the climate transitions may have driven cycles of enrichment and depletion of the deep-sea phosphorus reservoir. As temperature gradients in the oceans increased, Antarctic glaciation expanded and oceanic circulation and upwelling intensified. Expansion and intensification of the oxygen minimum zone may have increased the capacity for midwater storage of phosphorus supplied by dynamic upwelling around seamounts; however, the bottom waters never became anoxic during the phosphogenic episodes. Fluctuations in the CCD and lysocline, CO 2 fluxes, and changes in bottom water circulation and temperatures may have bathed the seamount carbonates in more corrosive waters which, coupled with increased supplies of dissolved phosphorus, promoted replacement processes. The late Eocene/early Oligocene phosphogenic episode recorded in seamount deposits is not matched by large phosphorite deposits in the geologic record, whereas the late Oligocene/early Miocene episode and middle Miocene event are matched by large deposits distributed globally. The seamount phosphorites are exposed at the surface of the seamounts and have been for most of the Neogene and Oligocene. The phosphorites do not show signs of etching that would indicate substantial undersaturation of seawater phosphate with respect to CFA. Mass balance calculations indicate that about 5.4–19 × 10 12 g of P 2 O 5 are locked up in equatorial Pacific seamount phosphorites. That amount is equivalent to about 2-7 years of the present annual input from rivers.

Paleoceanography and Paleoclimatology↗
USGS2010

Genesis of a regionally widespread celadonitic chert ironstone bed overlying upper Lias manganese deposits, Hungary

Mineralogy and chemical composition are presented for a chert-ironstone bed that overlies the ??rk??t Mn deposit. This bed is mottled green-brown in its lower and upper parts, which are composed of quartz, goethite and celadonite. These parts of the bed are interpreted to be strongly altered tuffs, reflecting oxidic, low-temperature alteration of a hydrated, Fe-rich, Al-poor tuff, and K and Mg uptake from seawater. The middle part of the bed is a mineralized bacterial mat (quartz, goethite). Textures resembling bacterial cells and colonies are common, with wavy, bulbous laminations composed of mounds overlying a mesh-work stromatolite-like texture constructed of micrometre-size Fe oxides. This bed is concordant with the underlying Mn deposit and marks the termination of Mn accumulation. Although no genetic connection exists between the two, the rocks adjacent to the contact record the oceanographic and bottom-water conditions extant when accumulation of one of the major Mn deposits of Europe ended, when the Transdanubian Range was located in the middle of the Adria-Apulian microcontinent between the Neotethys and Atlantic-Ligurian seaways. A pyroclastic origin for part of the bed has significance for the Toarcian of Central Europe because evidence of volcanism occurring at that time is otherwise sparse. ?? 2010 Geological Society of London.

Journal of the Geological Society↗
USGS2009

Thallium isotope evidence for a permanent increase in marine organic carbon export in the early Eocene

The first high resolution thallium (Tl) isotope records in two ferromanganese crusts (Fe-Mn crusts), CD29 and D11 from the Pacific Ocean are presented. The crusts record pronounced but systematic changes in 205Tl/203Tl that are unlikely to reflect diagenetic overprinting or changes in isotope fractionation between seawater and Fe-Mn crusts. It appears more likely that the Fe-Mn crusts track the Tl isotope composition of seawater over time. The present-day oceanic residence time of Tl is estimated to be about 20,000??yr, such that the isotopic composition should reflect ocean-wide events. New and published Os isotope data are used to construct age models for these crusts that are consistent with each other and significantly different from previous age models. Application of these age models reveals that the Tl isotope composition of seawater changed systematically between ~ 55??Ma and ~ 45??Ma. Using a simple box model it is shown that the present day Tl isotope composition of seawater depends almost exclusively on the ratio between the two principal output fluxes of marine Tl. These fluxes are the rate of removal of Tl from seawater via scavenging by authigenic Fe-Mn oxyhydroxide precipitation and the uptake rate of Tl during low temperature alteration of oceanic crust. It is highly unlikely that the latter has changed greatly. Therefore, assuming that the marine Tl budget has also not changed significantly during the Cenozoic, the low 205Tl/203Tl during the Paleocene is best explained by a more than four-fold higher sequestration of Tl by Fe-Mn oxyhydroxides compared with at the present day. The calculated Cenozoic Tl isotopic seawater curve displays a striking similarity to that of S, providing evidence that both systems may have responded to the same change in the marine environment. A plausible explanation is a marked and permanent increase in organic carbon export from ~ 55??Ma to ~ 45??Ma, which led to higher pyrite burial rates and a significantly reduced flux of Fe-Mn oxide removal as a result of increased biological uptake of Fe and Mn. ?? 2008 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters↗
USGS2009

Coral reef evolution on rapidly subsiding margins

A series of well-developed submerged coral reefs are preserved in the Huon Gulf (Papua New Guinea) and around Hawaii. Despite different tectonics settings, both regions have experienced rapid subsidence (2-6??m/ka) over the last 500??ka. Rapid subsidence, combined with eustatic sea-level changes, is responsible for repeated drowning and backstepping of coral reefs over this period. Because we can place quantitative constraints on these systems (i.e., reef drowning age, eustatic sea-level changes, subsidence rates, accretion rates, basement substrates, and paleobathymetry), these areas represent unique natural laboratories for exploring the roles of tectonics, reef accretion, and eustatic sea-level changes in controlling the evolution of individual reefs, as well as backstepping of the entire system. A review of new and existing bathymetric, radiometric, sedimentary facies and numerical modeling data indicate that these reefs have had long, complex growth histories and that they are highly sensitive, recording drowning not only during major deglaciations, but also during high-frequency, small-amplitude interstadial and deglacial meltwater pulse events. Analysis of five generalized sedimentary facies shows that reef drowning is characterized by a distinct biological and sedimentary sequence. Observational and numerical modeling data indicate that on precessional (20??ka) and sub-orbital timescales, the rate and amplitude of eustatic sea-level changes are critical in controlling initiation, growth, drowning or sub-aerial exposure, subsequent re-initiation, and final drowning. However, over longer timescales (> 100-500??ka) continued tectonic subsidence and basement substrate morphology influence broad scale reef morphology and backstepping geometries. Drilling of these reefs will yield greatly expanded stratigraphic sections compared with similar reefs on slowly subsiding, stable and uplifting margins, and thus they represent a unique archive of sea-level and climate changes, as well as a record of the response of coral reefs to these changes over the last six glacial cycles. ?? 2008 Elsevier B.V. All rights reserved.

Global and Planetary Change↗
USGS2009

Geophysical investigation of seamounts near the Ogasawara fracture zone, western Pacific

This paper provides an analysis of multi-channel seismic data obtained during 2000-2001 on seamounts near the Ogasawara Fracture Zone (OFZ) northwest of the Marshall Islands in the western Pacific. The OFZ is unique in that it is a wide rift zone that includes many seamounts. Seven units are delineated on the basis of acoustic characteristics and depth: three units (I, II, and III) on the summit of seamounts and four units (IV, V, VI, and VII) in basins. Acoustic characteristics of layers on the summit of guyots and dredged samples indicate that the seamounts had been built above sea level by volcanism. This was followed by reef growth along the summit margin, which enabled deposition of shallow-water carbonates on the summit, and finally by subsidence of the edifices. The subsidence depth of the seamounts, estimated from the lower boundary of unit II, ranges between 1,550 and 2,040 m. The thick unit I of the southern seamounts is correlated with proximity to the equatorial high productivity zone, whereas local currents may have strongly affected the distribution of unit I on northern seamounts. A seismic profile in the basin around the Ita Mai Tai and OSM4 seamounts shows an unconformity between units IV and V, which is widespread from the East Mariana Basin to the Pigafetta Basin. Copyright ?? The Society of Geomagnetism and Earth, Planetary and Space Sciences (SGEPSS); The Seismological Society of Japan; The Volcanological Society of Japan; The Geodetic Society of Japan; The Japanese Society for Planetary Sciences; TERRAPUB.

Earth, Planets and Space↗
USGS2008

Diffuse flow hydrothermal manganese mineralization along the active Mariana and southern Izu-Bonin arc system, western Pacific

Abundant ferromanganese oxides were collected along 1200 km of the active Izu-Bonin-Mariana arc system. Chemical compositions and mineralogy show that samples were collected from two deposit types: Fe-Mn crusts of mixed hydrogenetic/hydrothermal origin and hydrothermal Mn oxide deposits; this paper addresses only the second type. Mn oxides cement volcaniclastic and biogenic sandstone and breccia layers (Mn sandstone) and form discrete dense stratabound layers along bedding planes and within beds (stratabound Mn). The Mn oxide was deposited within coarse-grained sediments from diffuse flow systems where precipitation occurred below the seafloor. Deposits were exposed at the seabed by faulting, mass wasting, and erosion. Scanning electron microscopy and microprobe analyses indicate the presence of both amorphous and crystalline 10 ?? and 7 ?? manganate minerals, the fundamental chemical difference being high water contents in the amorphous Mn oxides. Alternation of amorphous and crystalline laminae occurs in many samples, which likely resulted from initial rapid precipitation of amorphous Mn oxides from waxing pulses of hydrothermal fluids followed by precipitation of slow forming crystallites during waning stages. The chemical composition is characteristic of a hydrothermal origin including strong fractionation between Fe (mean 0.9 wt %) and Mn (mean 48 wt %) for the stratabound Mn, generally low trace metal contents, and very low rare earth element and platinum group element contents. However, Mo, Cd, Zn, Cu, Ni, and Co occur in high concentrations in some samples and may be good indicator elements for proximity to the heat source or to massive sulfide deposits. For the Mn sandstones, Fe (mean-8.4%) and Mn (12.4%) are not significantly fractionated because of high Fe contents in the volcaniclastic material. However, the proportion of hydrothermal Fe (nondetrital Fe) to total Fe is remarkably constant (49-58%) for all the sample groups, regardless of the degree of Mn mineralization. Factor analyses indicate various mixtures of two dominant components: hydrothermal Mn oxide for the stratabound Mn and detrital aluminosilicate for the Mn-cemented sandstone; and two minor components, hydrothermal Fe oxyhydroxide and biocarbonate/biosilica. Our conceptual model shows that Mn mineralization was produced by hydrothermal convection cells within arc volcanoes and sedimentary prisms that occur along, the flanks and within calderas. The main source of hydrothermal fluid was seawater that penetrated through fractures, faults, and permeable volcanic edifices. The fluids were heated by magma, enriched in metals by leaching of basement rocks and sediments, and mixed with magmatic fluids and gases. Dikes and sills may have been another source of heat that drove small-scale circulation within sedimentary prisms. Copyright 2008 by the American Geophysical Union.

Journal of Geophysical Research B: Solid Earth↗
USGS2008

New constraints on the Pb and Nd isotopic evolution of NE Atlantic water masses

Time series of lead (Pb) and neodymium (Nd) isotope compositions were measured on three ferromanganese crusts recording the evolution of NE Atlantic water masses over the past 15 Ma. The crusts are distributed along a depth profile (∼700–4600 m) comprising the present-day depths of Mediterranean Outflow Water and North East Atlantic Deep Water. A pronounced increase of the 206 Pb/ 204 Pb in the two deeper crusts starting at ∼4 Ma and a decrease in 143 Nd/ 144 Nd in all three crusts took place between ∼6–4 Ma and the present. These patterns are similar to isotope time series in the western North Atlantic basin and are consistent with efficient mixing between the two basins. However, the changes occurred 1–3 Ma earlier in the eastern basin indicating that the northeastern Atlantic led the major change in Pb and Nd isotope composition, probably due to a direct supply of Labrador Seawater via a northern route. The Pb isotope evolution during the Pliocene-Pleistocene can generally be explained by mixing between two end-members corresponding to Mediterranean Outflow Water and North East Atlantic Deep Water, but external sources such as Saharan dust are likely to have played a role as well. The Pb isotope composition of the shallowest crust that grew within the present-day Mediterranean Outflow Water does not show significant Pb isotope changes indicating that it was controlled by the same Pb sources throughout the past 15 Ma.

Geochemistry, Geophysics, Geosystems↗
USGS2008

Seawater osmium isotope evidence for a middle Miocene flood basalt event in ferromanganese crust records

Three ferromanganese crusts from the northeast, northwest and central Atlantic were re-dated using osmium (Os) isotope stratigraphy and yield ages from middle Miocene to the present. The three Os isotope records do not show evidence for growth hiatuses. The reconstructed Os isotope-based growth rates for the sections older than 10??Ma are higher than those determined previously by the combined beryllium isotope (10Be/9Be) and cobalt (Co) constant-flux methods, which results in a decrease in the maximum age of each crust. This re-dating does not lead to significant changes to the interpretation of previously determined radiogenic isotope neodymium, lead (Nd, Pb) time series because the variability of these isotopes was very small in the records of the three crusts prior to 10??Ma. The Os isotope record of the central Atlantic crust shows a pronounced minimum during the middle Miocene between 15 and 12??Ma, similar to a minimum previously observed in two ferromanganese crusts from the central Pacific. For the other two Atlantic crusts, the Os isotope records and their calibration to the global seawater curve for the middle Miocene are either more uncertain or too short and thus do not allow for a reliable identification of an isotopic minimum. Similar to pronounced minima reported previously for the Cretaceous/Tertiary and Eocene/Oligocene boundaries, possible interpretations for the newly identified middle Miocene Os isotope minimum include changes in weathering intensity and/or a meteorite impact coinciding with the formation of the No??rdlinger Ries Crater. It is suggested that the eruption and weathering of the Columbia River flood basalts provided a significant amount of the unradiogenic Os required to produce the middle Miocene minimum. ?? 2008 Elsevier B.V.

Earth and Planetary Science Letters↗
USGS2008

Metalliferous sediment and a silica-hematite deposit within the Blanco fracture zone, Northeast Pacific

A Tiburon ROV dive within the East Blanco Depression (EBD) increased the mapped extent of a known hydrothermal field by an order of magnitude. In addition, a unique opal-CT (cristobalite-tridymite)-hematite mound was discovered, and mineralized sediments and rock were collected and analyzed. Silica-hematite mounds have not previously been found on the deep ocean floor. The light-weight rock of the porous mound consists predominantly of opal-CT and hematite filaments, rods, and strands, and averages 77.8% SiO2 and 11.8% Fe2O3. The hematite and opal-CT precipitated from a low-temperature (???115?? C), strongly oxidized, silica- and iron-rich, sulfur-poor hydrothermal fluid; a bacterial mat provided the framework for precipitation. Samples collected from a volcaniclastic rock outcrop consist primarily of quartz with lesser plagioclase, smectite, pyroxene, and sulfides; SiO2 content averages 72.5%. Formation of these quartz-rich samples is best explained by cooling in an up-flow zone of silica-rich hydrothermal fluids within a low permeability system. Opal-A, opal-CT, and quartz mineralization found in different places within the EBD hydrothermal field likely reflects decreasing silica saturation and increasing temperature of the mineralizing fluid with increasing silica crystallinity. Six push cores recovered gravel, coarse sand, and mud mineralized variously by Fe or Mn oxides, silica, and sulfides. Total rare-earth element concentrations are low for both the rock and push core samples. Ce and Eu anomalies reflect high and low temperature hydrothermal components and detrital phases. A remarkable variety of types of mineralization occur within the EBD field, yet a consistent suite of elements is enriched (relative to basalt and unmineralized cores) in all samples analyzed: Ag, Au, S, Mo, Hg, As, Sb, Sr, and U; most samples are also enriched in Cu, Pb, Cd, and Zn. On the basis of these element enrichments, the EBD hydrothermal field might best be described as a base- and precious-metal-bearing, silica-Fe-oxide-barite deposit. Such deposits are commonly spatially and temporally associated with volcanogenic massive sulfide (VMS) ores. A plot of data for pathfinder elements shows a large hot spot at the northwestern margin of the field, which may mark a region where moderate to high temperature sulfide deposits are forming at depth; further exploration of the hydrothermal field to the northwest is warranted.

Marine Georesources and Geotechnology↗
USGS2007

Platinum group elements and gold in ferromanganese crusts from Afanasiy-Nikitin seamount, equatorial Indian Ocean: Sources and fractionation

The major element relationships in ferromanganese (Fe-Mn) crusts from Afanasiy-Nikitin seamount (ANS), eastern equatorial Indian Ocean, appear to be atypical. High positive correlations ( r = 0.99) between Mn/Co and Fe/Co ratios, and lack of correlation of those ratios with Co, Ce, and Ce/Co, indicate that the ANS Fe-Mn crusts are distinct from Pacific seamount Fe-Mn crusts, and reflect region-specific chemical characteristics. The platinum group elements (PGE: Ir, Ru, Rh, Pt, and Pd) and Au in ANS Fe-Mn crusts are derived from seawater and are mainly of terrestrial origin, with a minor cosmogenic component. The Ru/Rh (0.5–2) and Pt/Ru ratios (7–28) are closely comparable to ratios in continental basalts, whereas Pd/Ir ratios exhibit values (<2) similar to CI-chondrite (∼1). The chondrite-normalized PGE patterns are similar to those of igneous rocks, except that Pd is relatively depleted. The water depth of Fe-Mn crust formation appears to have a first-order control on both major element and PGE enrichments. These relationships are defined statistically by significant ( r > 0.75) correlations between water depth and Mn/Co, Fe/Co, Ce/Co, Co, and the PGEs. Fractionation of the PGE-Au from seawater during colloidal precipitation of the major-oxide phases is indicated by well-defined linear positive correlations ( r > 0.8) of Co and Ce with Ir, Ru, Rh, and Pt; Au/Co with Mn/Co; and by weak or no correlations of Pd with water depth, Co-normalized major-element ratios, and with the other PGE ( r < 0.5). The strong enrichment of Pt (up to 1 ppm) relative to the other PGE and its positive correlations with Ce and Co demonstrate a common link for the high concentrations of all three elements, which likely involves an oxidation reaction on the Mn-oxide and Fe-oxyhydroxide surfaces. The documented fractionation of PGE-Au and their positive association with redox sensitive Co and Ce may have applications in reconstructing past-ocean redox conditions and water masses.

Journal of Earth System Science↗
USGS2007

Lithium contents and isotopic compositions of ferromanganese deposits from the global ocean

To test the feasibility of using lithium isotopes in marine ferromanganese deposits as an indicator of paleoceanographic conditions and seawater composition, we analyzed samples from a variety of tectonic environments in the global ocean. Hydrogenetic, hydrothermal, mixed hydrogenetic–hydrothermal, and hydrogenetic–diagenetic samples were subjected to a two-step leaching and dissolution procedure to extract first the loosely bound Li and then the more tightly bound Li in the Mn oxide and Fe oxyhydroxide. Total leachable Li contents vary from <1 ppm in hydrogenetic crusts to 1422 ppm (up to 1188 ppm measured here) in hydrothermal deposits. Hydrated Li ions in seawater and hydrothermal fluids are preferentially sorbed on the negatively charged surface of MnO 2 by coulombic force. Hence, the abundant Li in hydrothermal deposits is mainly associated with the dominant phase, MnO 2 . The surface of amorphous FeOOH holds a slightly positive charge and attracts little Li, as demonstrated by data for hydrothermal Fe oxyhydroxide. Loosely sorbed Li in both hydrogenetic crusts and hydrothermal deposits exhibit Li isotopic compositions that resemble that of modern seawater. We infer that the hydrothermally derived Li scavenged onto the surface of MnO 2 freely exchanged with ambient seawater, thereby losing its original isotopic signature. Li in the tightly bound sites is always isotopically lighter than that in the loosely bound fraction, suggesting that the isotopic fractionation occurred during formation of chemical bonds in the oxide and oxyhydroxide structures. Sr isotopes also show evidence of re-equilibration with seawater after deposition. Because of their mobility, Li and Sr in the ferromanganese crusts do not faithfully record secular variations in the isotopic compositions of seawater. However, Li content can be a useful proxy for the hydrothermal history of ocean basins. Based on the Li concentrations of the globally distributed hydrogenetic and hydrothermal samples, we estimate a scavenging flux of Li that is insignificant compared to the hydrothermal flux and river input to the ocean.

Deep-Sea Research Part II: Topical Studies in Ocea↗
USGS2006

Helium isotopes in ferromanganese crusts from the central Pacific Ocean

Helium isotopes have been measured in samples of two ferromanganese crusts (VA13/2 and CD29-2) from the central Pacific Ocean. With the exception of the deepest part of crust CD29-2 the data can be explained by a mixture of implanted solar- and galactic cosmic ray-produced (GCR) He, in extraterrestrial grains, and radiogenic He in wind-borne continental dust grains. 4 He concentrations are invariant and require retention of less than 12% of the in situ He produced since crust formation. Loss has occurred by recoil and diffusion. High 4 He in CD29-2 samples older than 42 Ma are correlated with phosphatization and can be explained by retention of up to 12% of the in situ-produced 4 He. 3 He/ 4 He of VA13/2 samples varies from 18.5 to 1852 Ra due almost entirely to variation in the extraterrestrial He contribution. The highest 3 He/ 4 He is comparable to the highest values measured in interplanetary dust particles (IDPs) and micrometeorites (MMs). Helium concentrations are orders of magnitude lower than in oceanic sediments reflecting the low trapping efficiency for in-falling terrestrial and extraterrestrial grains of Fe-Mn crusts. The extraterrestrial 3 He concentration of the crusts rules out whole, undegassed 4–40 μm diameter IDPs as the host. Instead it requires that the extraterrestrial He inventory is carried by numerous particles with significantly lower He concentrations, and occasional high concentration GCR-He-bearing particles.

Geochimica et Cosmochimica Acta↗