Geology topics

J.R. Hein

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

At least 37 records · Page 2Linked to original sources

USGS2004

Deep and bottom water export from the Southern Ocean to the Pacific over the past 38 million years

The application of radiogenic isotopes to the study of Cenozoic circulation patterns in the South Pacific Ocean has been hampered by the fact that records from only equatorial Pacific deep water have been available. We present new Pb and Nd isotope time series for two ferromanganese crusts that grew from equatorial Pacific bottom water (D137-01, "Nova," 7219 m water depth) and southwest Pacific deep water (63KD, "Tasman," 1700 m water depth). The crusts were dated using 10 Be/ 9 Be ratios combined with constant Co-flux dating and yield time series for the past 38 and 23 Myr, respectively. The surface Nd and Pb isotope distributions are consistent with the present-day circulation pattern, and therefore the new records are considered suitable to reconstruct Eocene through Miocene paleoceanography for the South Pacific. The isotope time series of crusts Nova and Tasman suggest that equatorial Pacific deep water and waters from the Southern Ocean supplied the dissolved trace metals to both sites over the past 38 Myr. Changes in the isotopic composition of crust Nova are interpreted to reflect development of the Antarctic Circumpolar Current and changes in Pacific deep water circulation caused by the build up of the East Antarctic Ice Sheet. The Nd isotopic composition of the shallower water site in the southwest Pacific appears to have been more sensitive to circulation changes resulting from closure of the Indonesian seaway.

Paleoceanography↗

USGS2004

Tracing the history of submarine hydrothermal inputs and the significance of hydrothermal hafnium for the seawater budget - A combined Pb-Hf-Nd isotope approach

Secular variations in the Pb isotopic composition of a mixed hydrogenous-hydrothermal ferromanganese crust from the Bauer Basin in the eastern Equatorial Pacific provide clear evidence for changes in hydrothermal contributions during the past 7 Myr. The nearby Galapagos Rise spreading center provided a strong hydrothermal flux prior to 6.5 Ma. After 6.5 Ma, the Pb became stepwise more radiogenic and more similar to Equatorial Pacific seawater, reflecting the westward shift of spreading to the presently active East Pacific Rise (EPR). A second, previously unrecognized enhanced hydrothermal period occurred between 4.4 and 2.9 Ma, which reflects either off-axis hydrothermal activity in the Bauer Basin or a late-stage pulse of hydrothermal Pb from the then active, but waning Galapagos Rise spreading center. Hafnium isotope time-series of the same mixed hydrogenous-hydrothermal crust show invariant values over the past 7 Myr. Hafnium isotope ratios, as well as Nd isotope ratios obtained for this crust, are identical to that of hydrogenous Equatorial Pacific deep water crusts and clearly indicate that hydrothermal Hf, similar to Nd, does not travel far from submarine vents. Therefore, we suggest that hydrothermal Hf fluxes do not contribute significantly to the global marine Hf budget. ?? 2004 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters↗

USGS2004

The global variation in the iron isotope composition of marine hydrogenetic ferromanganese deposits: Implications for seawater chemistry?

The iron (Fe) isotope compositions of 37 hydrogenetic ferromanganese deposits from various oceans have been analysed by MC-ICPMS; they permit the construction of a global map of Fe isotopic values. The isotopic compositions range between -1.2 and -0.1??? in ??57FeIRMM14. Averages for the Atlantic and the Pacific are -0.41 and -0.88???, but their standard deviations are identical (0.27, 1 ??) and the data very largely overlap. No correlation is found with Pb or Nd isotope compositions and there is no evidence that the observed oceanic Fe isotopic heterogeneity is directly controlled by variations in continental sources. The small quantities of Fe that can be introduced from hydrothermal sources render as unlikely the possibility that the isotopic variations reflect variable proportions of continental and hydrothermal Fe, as recently proposed. The more likely explanation is that the variations are induced locally within the ocean. The exact sources of fractionation remain unclear. Likely possibilities are the dissolution and reprecipitation processes that liberate Fe from sediments during anoxic events, dissolution in surface waters or processes occurring during growth of the crusts. ?? 2004 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters↗

USGS2003

Lead isotopes in North Pacific deep water - Implications for past changes in input sources and circulation patterns

The sources of non-anthropogenic Pb in seawater have been the subject of debate. Here we present Pb isotope time-series that indicate that the non-anthropogenic Pb budget of the northernmost Pacific Ocean has been governed by ocean circulation and riverine inputs, which in turn have ultimately been controlled by tectonic processes. Despite the fact that the investigated locations are situated within the Asian dust plume, and proximal to extensive arc volcanism, eolian contributions have had little impact. We have obtained the first high-resolution and high-precision Pb isotope time-series of North Pacific deep water from two ferromanganese crusts from the Gulf of Alaska in the NE Pacific Ocean, and from the Detroit Seamount in the NW Pacific Ocean. Both crusts were dated applying 10 Be/9Be ratios and yield continuous time-series for the past 13.5 and 9.6 Myr, respectively. Lead isotopes show a monotonic evolution in 206Pb/204Pb from low values in the Miocene (??? 18.57) to high values at present day (??? 18.84) in both crusts, even though they are separated by more than 3000 km along the Aleutian Arc. The variation exceeds the amplitude found in Equatorial Pacific deep water records by about three-fold. There also is a striking similarity in 207Pb/204Pb and 208Pb/ 204Pb ratios of the two crusts, indicating the existence of a local circulation cell in the sub-polar North Pacific, where efficient lateral mixing has taken place but only limited exchange (in terms of Pb) with deep water from the Equatorial Pacific has occurred. Both crusts display well-defined trends with age in Pb-Pb isotope mixing plots, which require the involvement of at least four distinct Pb sources for North Pacific deep water. The Pb isotope time-series reveal that eolian supplies (volcanic ash and continent-derived loess) have only been of minor importance for the dissolved Pb budget of marginal sites in the deep North Pacific over the past 6 Myr. The two predominant sources have been young volcanic arcs, one located in the northeastern part and one located in the northwestern part of the Pacific margin, from where material has been eroded and delivered to the ocean, most likely via riverine pathways. ?? 2003 Elsevier Science B.V. All rights reserved.

Earth and Planetary Science Letters↗

USGS2003

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element. We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases. Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO 2 , carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO 2 . Thermodynamic calculations indicate that Te occurs predominantly as H 5 TeO 6 − in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO 2 in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.

Geochimica et Cosmochimica Acta↗

USGS2003

Clay-mineral suites, sources, and inferred dispersal routes: Southern California continental shelf

Clay mineralogy is useful in determining the distribution, sources, and dispersal routes of fine-grained sediments. In addition, clay minerals, especially smectite, may control the degree to which contaminants are adsorbed by the sediment. We analyzed 250 shelf sediment samples, 24 river-suspended-sediment samples, and 12 river-bed samples for clay-mineral contents in the Southern California Borderland from Point Conception to the Mexico border. In addition, six samples were analyzed from the Palos Verdes Headland in order to characterize the clay minerals contributed to the offshore from that point source. The <2 ??m-size fraction was isolated, Mg-saturated, and glycolated before analysis by X-ray diffraction. Semi-quantitative percentages of smectite, illite, and kaolinite plus chlorite were calculated using peak areas and standard weighting factors. Most fine-grained sediment is supplied to the shelf by rivers during major winter storms, especially during El Nin??o years. The largest sediment fluxes to the region are from the Santa Ynez and Santa Clara Rivers, which drain the Transverse Ranges. The mean clay-mineral suite for the entire shelf sediment data set (26% smectite, 50% illite, 24% kaolinite+chlorite) is closely comparable to that for the mean of all the rivers (31% smectite, 49% illite, 20% kaolinite+chlorite), indicating that the main source of shelf fine-grained sediments is the adjacent rivers. However, regional variations do exist and the shelf is divided into four provinces with characteristic clay-mineral suites. The means of the clay-mineral suites of the two southernmost provinces are within analytical error of the mineral suites of adjacent rivers. The next province to the north includes Santa Monica Bay and has a suite of clay minerals derived from mixing of fine-grained sediments from several sources, both from the north and south. The northernmost province clay-mineral suite matches moderately well that of the adjacent rivers, but does indicate some mixing from sources in adjacent provinces.

Marine Environmental Research↗

USGS2002

North Atlantic Deep Water export to the Southern Ocean over the past 14 Myr: Evidence from Nd and Pb isotopes in ferromanganese crusts

The intensity of North Atlantic Deep Water (NADW) production has been one of the most important parameters controlling the global thermohaline ocean circulation system and climate. Here we present a new approach to reconstruct the overall strength of NADW export from the North Atlantic to the Southern Ocean over the past 14 Myr applying the deep water Nd and Pb isotope composition as recorded by ferromanganese crusts and nodules. We present the first long-term Nd and Pb isotope time series for deep Southern Ocean water masses, which are compared with previously published time series for NADW from the NW Atlantic Ocean. These data suggest a continuous and strong export of NADW, or a precursor of it, into the Southern Ocean between 14 and 3 Ma. An increasing difference in Nd and Pb isotope compositions between the NW Atlantic and the Southern Ocean over the past 3 Myr gives evidence for a progressive overall reduction of NADW export since the onset of Northern Hemisphere glaciation (NHG). The Nd isotope data allow us to assess at least semiquantitatively that the amount of this reduction has been in the range between 14 and 37% depending on location.

Paleoceanography↗

USGS2002

Thallium isotope variations in seawater and hydrogenetic, diagenetic, and hydrothermal ferromanganese deposits

Results are presented for the first in-depth investigation of TI isotope variations in marine materials. The TI isotopic measurements were conducted by multiple collector-inductively coupled plasma mass spectrometry for a comprehensive suite of hydrogenetic ferromanganese crusts, diagenetic Fe-Mn nodules, hydrothermal manganese deposits and seawater samples. The natural variability of TI isotope compositions in these samples exceeds the analytical reproducibility (?? 0.05???) by more than a factor of 40. Hydrogenetic Fe-Mn crusts have ??205TI of + 10 to + 14, whereas seawater is characterized by values as low as -8 (??205TI represents the deviation of the 205TI/203TI ratio of a sample from the NIST SRM 997 TI isotope standard in parts per 104). This ~ 2??? difference in isotope composition is thought to result from the isotope fractionation that accompanies the adsorption of TI onto ferromanganese particles. An equilibrium fractionation factor of ?? ~ 1.0021 is calculated for this process. Ferromanganese nodules and hydrothermal manganese deposits have variable TI isotope compositions that range between the values obtained for seawater and hydrogenetic Fe-Mn crusts. The variability in ??205TI in diagenetic nodules appears to be caused by the adsorption of TI from pore fluids, which act as a closed-system reservoir with a TI isotope composition that is inferred to be similar to seawater. Nodules with ??205TI values similar to seawater are found if the scavenging of TI is nearly quantitative. Hydrothermal manganese deposits display a positive correlation between ??205TI and Mn/Fe. This trend is thought to be due to the derivation of TI from distinct hydrothermal sources. Deposits with low Mn/Fe ratios and low ??205TI are produced by the adsorption of TI from fluids that are sampled close to hydrothermal sources. Such fluids have low Mn/Fe ratios and relatively high temperatures, such that only minor isotope fractionation occurs during adsorption. Hydrothermal manganese deposits with high Mn/Fe and high ??205Ti are generated by scavenging of TI from colder, more distal hydrothermal fluids. Under such conditions, adsorption is associated with significant isotope fractionation, and this produces deposits with higher ??205TI values coupled with high Mn/Fe. ?? 2002 Elsevier Science B.V. All rights reserved.

Earth and Planetary Science Letters↗

USGS2000

Growth response of a deep-water ferromanganese crust to evolution of the Neogene Indian Ocean

A deep-water ferromanganese crust from a Central Indian Ocean seamount dated previously by 10Be and 230Th(excess) was studied for compositional and textural variations that occurred throughout its growth history. The 10Be/9Be dated interval (upper 32 mm) yields an uniform growth rate of 2.8 ?? 0.1 mm/Ma [Frank, M., O'Nions, R.K., 1998. Sources of Pb for Indian Ocean ferromanganese crusts: a record of Himalayan erosion. Earth Planet. Sci. Lett., 158, pp. 121-130.] which gives an extrapolated age of ~ 26 Ma for the base of the crust at 72 mm and is comparable to the maximum age derived from the Co-model based growth rate estimates. This study shows that Fe-Mn oxyhydroxide precipitation did not occur from the time of emplacement of the seamount during the Eocene (~ 53 Ma) until the late Oligocene (~ 26 Ma). This paucity probably was the result of a nearly overlapping palaeo-CCD and palaeo-depth of crust formation, increased early Eocene productivity, instability and reworking of the surface rocks on the flanks of the seamount, and lack of oxic deep-water in the nascent Indian Ocean. Crust accretion began (older zone) with the formation of isolated cusps of Fe-Mn oxide during a time of high detritus influx, probably due to the early-Miocene intense erosion associated with maximum exhumation of the Himalayas (op. cit.). This cuspate textured zone extends from 72 mm to 42 mm representing the early-Miocene period. Intense polar cooling and increased mixing of deep and intermediate waters at the close of the Oligocene might have led to the increased oxygenation of the bottom-water in the basin. A considerable expansion in the vertical distance between the seafloor depth and the CCD during the early Miocene in addition to the influx of oxygenated bottom-water likely initiated Fe-Mn crust formation. Pillar structure characterises the younger zone, which extends from 40 mm to the surface of the crust, i.e., ~ 15 Ma to Present. This zone is characterised by > 25% higher content of oxide-bound elements than in the older zone, possibly corresponding to further increased oxygenation of bottom-waters, increased stability of the seamount slope, and gradually reduced input of continental detritus from the erosion of the Himalayas. Middle Miocene Antarctic glaciation, which peaked ~ 12-13 Ma ago, increased the oxic bottom-water influx to the basin resulting in accretion of the crust with low detritus. Therefore, the younger crust started to accrete in response to a shift in bottom-water circulation towards the contemporary pattern, which produced a uniform growth rate and pillar structure up to the present. (C) 2000 Published by Elsevier Science B.V.

Marine Geology↗

USGS2000

Formation of ferromanganese crusts on northwest intertropical Pacific seamounts: Electron photomicrography and microprobe chemistry

Seven ferromanganese crusts from the northwest intertropical Pacific seamounts were analyzed for photomicroscopic growth structures, microprobe chemistry, and ages based on Co-chronometer growth rate. The crusts on the Marshall Islands seamounts are thick and ale divided into phosphatized lower older and nonphosphatized upper younger growth generations: the older crust consists of compact laminations and columns impregnated with carbonate fluoapatite (CFA), whereas the younger crust is characterized by porous botryoids and columns of ??-MnO2 and Fe oxyhydroxide. The crusts on the Federated States of Micronesia (FSM) and Palau Islands seamounts are thin and are often incorporated with inorganic opal-A in the uppermost part, comprising the younger generation. Some crusts show scours and fractures. Although the growth of crusts has been often interrupted by mass failure of slope sediments, the crusts on the Marshall Islands seamounts are estimated to have grown at rate of about 3 mm/Ma since the middle Eocene and to have been phosphatized in the late Oligocene during the host seamounts were located beneath the equatorial zone of high productivity. Prolonged infiltration of the oxygen minimum zone (OMZ) water into shallower water older crusts redistributed crust composition by precipitating CFA, enriching subsequent amounts of Mn and Ni, and removing some Co. The younger crust has formed at slower rate (about 2 mm/Ma) under the stronger influence of bottom-water circulation in the north of the equatorial zone, concentrating abundant Co. In the uppermost part of some crusts, siliceous skeletons transform with burial to inorganic opal-A and Si-rich Fe oxyhydroxide, suggesting that biosilica diagenesis can enhance crust growth. (C) 2000 Elsevier Science B.V.

Marine Geology↗

USGS1999

60 Myr records of major elements and Pb-Nd isotopes from hydrogenous ferromanganese crusts: Reconstruction of seawater paleochemistry

We compare the time series of major element geochemical and Pb- and Nd-isotopic composition obtained for seven hydrogenous ferromanganese crusts from the Atlantic, Indian, and Pacific Oceans which cover the last 60 Myr. Average crust growth rates and age-depth relationships were determined directly for the last about 10 Myr using 10Be/9Be profiles. In the absence of other information these were extrapolated to the base of the crusts assuming constant growth rates and constant initial 10Be/9Be ratios due to the lack of additional information. Co contents have also been used previously to estimate growth rates in Co-rich Pacific and Atlantic seamount crusts (Puteanus and Halbach, 1988). A comparison of 10Be/9Be- and Co-based dating of three Co-rich crusts supports the validity of this approach and confirms the earlier chronologies derived from extrapolated 10Be/9Be-based growth rates back to 60 Ma. Our data show that the flux of Co into Co-poor crusts has been considerably lower. The relationship between growth rate and Co content for the Co-poor crusts developed from these data is in good agreement with a previous study of a wider range of marine deposits (Manheim, 1986). The results suggest that the Co content provides detailed information on the growth history of ferromanganese crusts, particularly prior to 10-12 Ma where the 10Be-based method is not applicable. The distributions of Pb and Nd isotopes in the deep oceans over the last 60 Myr are expected to be controlled by two main factors: (a) variations of oceanic mixing patterns and flow paths of water masses with distinct isotopic signatures related to major paleogeographic changes and (b) variability of supply rates or provenance of detrital material delivered to the ocean, linked to climate change (glaciations) or major tectonic uplift. The major element profiles of crusts in this study show neither systematic features which are common to crusts with similar isotope records nor do they generally show coherent relationships to the isotope records within a single crust. Consequently, any interpretation of time series of major element concentrations of a single crust in terms of paleoceanographic variations must be considered with caution. This is because local processes appear to have dominated over more basin-wide paleoceanographic effects. In this study Co is the only element which shows a relationship to Pb and Nd isotopes in Pacific crusts. A possible link to changes of Pacific deep water properties associated with an enhanced northward advection of Antarctic bottom water from about 14 Ma is consistent with the Pb but not with the Nd isotopic results. The self-consistent profiles of the Pb and Nd isotopes suggest that postdepositional diagenetic processes in hydrogenous crusts, including phosphatization events, have been insignificant for particle reactive elements such as Pb, Be, and Nd. Isotope time series of Pb and Nd show no systematic relationships with major element contents of the crusts, which supports their use as tracers of paleo-seawater isotopic composition.

Geochimica et Cosmochimica Acta↗

USGS1999

Composition and origin of Early Cambrian Tiantaishan phosphorite-Mn carbonate ores, Shaanxi Province, China

The Tiantaishan phosphorite-Mn carbonate ores occur in the Early Cambrian Tananpo Formation in complexly folded and faulted rocks located in southern Shaanxi Province. About 65 x 106 tonnes of 17% P2O5 ore reserves exist and Mn-ore reserves are about 8.3 x 106 tonnes of +18% Mn. The stratigraphic sequence in ascending order consists of black phyllite, black to gray phosphorite ore, black phyllite, rhodochrostone ore, Mn mixed-carbonates, and dolostone. Data are presented from microprobe mineral chemistry, whole-rock chemistry, stable isotopes of carbonates, X-ray mineralogy, petrographic and SEM observations, and statistical analysis of chemical data. The dominant ore-forming minerals are hydroxy- and carbonate fluorapatite and Ca rhodochrosite, with Mg kutnahorite and dolomite comprising the Mn mixed-carbonate section. Pyrite occurs in all rock types and alabandite (MnS) occurs throughout the rhodochrostone section. The mean P2O5 content of phosphorite is 31% and argillaceous phosphorite is 16%, while the mean MnO content of rhodochrostone ore is 37%. Phosphorite ores are massive, spheroidal, laminated, and banded, while rhodochrostone ores have oolitic, spheroidal, and granular fabrics. The most distinguishing characteristics of the ores are high total organic carbon (TOC) contents (mean 8.4%) in the phosphorite and high P2O5 contents (mean 2.7%) in the rhodochrostone ore. The atypically high TOC contents in the Tiantaishan phosphorite probably result from very strong productivity leading to high sedimentation rates accompanied by weak reworking of sediments; poor utilization of the organic matter by bacteria; and/or partial replacement of bacterial or algal mats by the apatite. The depositional setting of the ores was the margin of an epicontinental seaway created as a direct consequence of global processes that included break-up of a supercontinent, formation of narrow seaways, creation of extensive continental shelves, overturn of stagnant, metal-rich deep-ocean waters, and marine transgression. Water depth increased from deposition of the black phyllite sequence through deposition of the Mn mixed-carbonate sequence, then shallowed again during deposition of the overlying dolostone sequence. Bottom waters were mostly dysoxic to suboxic, but fluctuated from oxic to anoxic. Productivity was high during deposition of the black phyllite sequence, increased during precipitation of phosphorite, and then decreased to moderate levels during precipitation of rhodochrostone ores. Biosilica contributions occur in each lithology, but are greatest in rhodochrostone. Changes in sedimentation were determined by changes in water depth, productivity, upwelling, sea-level change, and ventilation of the depositional basin. The source of the phosphorus was organic matter produced in great quantities during deposition of the black phyllite and phosphorite sequences in a zone of coastal upwelling. Organic matter accumulation was rapid. Globally, Mn was supplied by overturn of stagnant, metal-rich deep-ocean waters, which were redistributed to areas of coastal upwelling and seaways; that process may have been initiated by latest Proterozoic glaciations which would have promoted density stratification and accumulation and storage of metals. Regionally, Mn was supplied by terrigenous input into the shallow seaway and hydrothermal input into the deeper water parts of that seaway. Locally, Mn sources included leaching and transport of metals from the sediment column. Manganese was stored locally in low-oxygen (not anoxic) seawater prior to Mn-ore formation. The source of the carbon in the Mn carbonates and dolostones was predominantly seawater bicarbonate and secondarily CO2 derived from the oxidation of organic matter in the bacterially mediated diagenetic zone of sulfate reduction.

Ore Geology Reviews↗

USGS1999

Influence of substrate rocks on Fe-Mn crust composition

Principal Component and other statistical analyses of chemical and mineralogical data of Fe-Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.

Deep-Sea Research Part I: Oceanographic Research P↗

USGS1999

Hafnium isotope stratigraphy of ferromanganese crusts

A Cenozoic record of hafnium isotopic compositions of central Pacific deep water has been obtained from two ferromanganese crusts. The crusts are separated by more than 3000 kilometers but display similar secular variations. Significant fluctuations in hafnium isotopic composition occurred in the Eocene and Oligocene, possibly related to direct advection from the Indian and Atlantic oceans. Hafnium isotopic compositions have remained approximately uniform for the past 20 million years, probably reflecting increased isolation of the central Pacific. The mechanisms responsible for the increase in 87Sr/86Sr in seawater through the Cenozoic apparently had no effect on central Pacific deep-water hafnium.

Science↗

USGS1997

Evolution of Nd and Pb isotopes in Central Pacific seawater from ferromanganese crusts

Hydrogenetic ferromanganese crusts incorporate elements from ambient seawater during their growth on seamounts. By analysing Nd, Pb and Be isotope profiles within crusts it is possible to reconstruct seawater tracer histories. Depth profiles of 10 Be/ 9 Be ratios in three Pacific ferromanganese crusts have been used to obtain growth rates which are between 1.4 and 3.8 mm/Ma. Nd and Pb isotopes provide intact records of isotopic variations in Pacific seawater over the last 20 Ma or more. There were only small changes in Pb isotope composition in the last 20 Ma. This indicates a constant Pb composition for the erosional sources and suggests further that erosional Nd inputs may have been uniform too. ε Nd values vary considerably with time and most probably reflect changes in ocean circulation. The ε Nd values of the crusts not only vary as a function of age but also as a function of water depth. From 25 to 0 Ma, crust VA13/2 from 4.8 km water depth has a similar pattern of ε Nd variation to the two shallower crusts from 1.8 and 2.3 km, but about 1.0 to 1.5 units more negative. This suggests that ε Nd stratification in Pacific seawater, as demonstrated for the present day, has been maintained for at least 20 Ma. Each crust shows a decrease in ε Nd from 3–5 Ma to the present, which is interpreted in terms of an increase in the NADW component present in the Pacific. From 10 to 3–5 Ma ago the crusts show an increase in ε Nd . This suggests a decreasing role for a deep water source with ε Nd less than circum-Pacific sources. In this regard the Panamanian gateway restriction from ∼ 10 Ma with final closure at 3–5 Ma may have played an important role in reducing access of Atlantic-derived Nd to the Pacific.

Earth and Planetary Science Letters↗

USGS1997

238U-234U-230Th disequilibrium in hydrogenous oceanic Fe-Mn crusts: Palaeoceanographic record or diagenetic alteration?

A detailed TIMS study of ( 234 U exc / 238 U), ( 230 Th/ 232 Th), and Th/U ratios have been performed on the outermost margin of ten hydrogenous Fe Mn crusts from the equatorial Pacific Ocean and west-central Indian Ocean.Th/U concentration ratios generally decrease from the crust's surface down to 0.5-1 mm depth and growth rates estimated by uranium and thorium isotope ratios are significantly different in Fe Mn crusts from the Peru Basin and the west-central Indian Ocean. Fe Mn crusts from the same geographical area define a single trend in plots of Ln( 234 U exc / 238 U) vs. Ln( 230 Th/ 232 Th) and Th/U ratios vs. age of the analysed fractions. Results suggest that (l) hydrogenous Fe Mn crusts remain closed-systems after formation, and consequently (2) the discrepancy observed between the 230 Th and 234U chronometers in Fe Mn crusts, and the variations of the Th/U ratios through the margin of FeMn crusts, are not due to redistribution of uranium and thorium isotopes after oxyhydroxide precipitation, but rather to temporal variations of both Th/U and initial thorium activity ratios recorded by the Fe Mn layers. Implications of these observations for determination of Fe Mn crust growth-rates are discussed. Variations of both Th/U and initial Th activity ratios in Fe Mn crusts might be related to changes in particle input to seawater and/or changes in ocean circulation during the last 150 ka.

Geochimica et Cosmochimica Acta↗

USGS1996

Iron and manganese oxide mineralization in the Pacific

Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. Iron and manganese deposits occur in five forms: nodules, crusts, cements, mounds and sediment-hosted stratabound layers. Seafloor oxides show a wide range of compositions from nearly pure iron to nearly pure manganese end members. Fe/Mn ratios vary from about 24 000 (up to 58% elemental Fe) for hydrothermal seamount ironstones to about 0.001 (up to 52% Mn) for hydrothermal stratabound manganese oxides from active volcanic arcs. Hydrogenetic Fe-Mn crusts that occur on most seamounts in the ocean basins have a mean Fe/Mn ratio of 0.7 for open-ocean seamount crusts and 1.2 for continental margin seamount crusts. Fe-Mn nodules of potential economic interest from the Clarion-Clipperton Zone have a mean Fe/Mn ratio of 0.3, whereas the mean ratio for nodules from elsewhere in the Pacific is about 0.7. Crusts are enriched in Co, Ni and Pt and nodules in Cu and Ni, and both have significant concentrations of Pb, Zn, Ba, Mo, V and other elements. In contrast, hydrothermal deposits commonly contain only minor trace metal contents, although there are many exceptions, for example, with Ni contents up to 0.66%, Cr to 1.2%, and Zn to 1.4%. Chondrite-normalized REE patterns generally show a positive Ce anomaly and abundant ΣREEs for hydrogenetic and mixed hydrogenetic-diagenetic deposits, whereas the Ce anomaly is negative for hydrothermal deposits and ΣREE contents are low. However, the Ce anomaly in crusts may vary from strongly positive in East Pacific crusts to slightly negative in West Pacific crusts, which may reflect the redox conditions of seawater. The concentration of elements in hydrogenetic Fe-Mn crusts depends on a wide variety of water column and crust surface characteristics, whereas concentration of elements in hydrothermal oxide deposits depends of the intensity of leaching, rock types leached, and precipitation of sulphides at depth in the hydrothermal system.

Geological Society Special Publication↗

USGS1996

The zeolite deposits of Greece

Zeolites are present in altered pyroclastic rocks at many localities in Greece, and large deposits of potential economic interest are present in three areas: (1) the Evros region of the province of Thrace in the north-eastern part of the Greek mainland; (2) the islands of Kimolos and Poliegos in the western Aegean; and (3) the island of Samos in the eastern Aegean Sea. The deposits in Thrace are of Eocene-Oligocene age and are rich in heulandite and/or clinoptilolite. Those of Kimolos and Poliegos are mainly Quaternary and are rich in mordenite. Those of Samos are Miocene, and are rich in clinoptilolite and/or analcime. The deposits in Thrace are believed to have formed in an open hydrological system by the action of meteoric water, and those of the western Aegean islands in a similar way but under conditions of high heat flow, whereas the deposits in Samos were formed in a saline-alkaline lake.

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