Geology topics

J.R. Hein

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

At least 37 records · Page 2Linked to original sources

USGS2006

Long-term eruptive activity at a submarine arc volcano

Three-quarters of the Earth's volcanic activity is submarine, located mostly along the mid-ocean ridges, with the remainder along intraoceanic arcs and hotspots at depths varying from greater than 4,000 m to near the sea surface. Most observations and sampling of submarine eruptions have been indirect, made from surface vessels or made after the fact. We describe here direct observations and sampling of an eruption at a submarine arc volcano named NW Rota-1, located 60 km northwest of the island of Rota (Commonwealth of the Northern Mariana Islands). We observed a pulsating plume permeated with droplets of molten sulphur disgorging volcanic ash and lapilli from a 15-m diameter pit in March 2004 and again in October 2005 near the summit of the volcano at a water depth of 555 m (depth in 2004). A turbid layer found on the flanks of the volcano (in 2004) at depths from 700 m to more than 1,400 m was probably formed by mass-wasting events related to the eruption. Long-term eruptive activity has produced an unusual chemical environment and a very unstable benthic habitat exploited by only a few mobile decapod species. Such conditions are perhaps distinctive of active arc and hotspot volcanoes. ?? 2006 Nature Publishing Group.

Nature↗

USGS2006

Methanogenic calcite, 13C-depleted bivalve shells, and gas hydrate from a mud volcano offshore southern California

Methane and hydrogen sulfide vent from a cold seep above a shallowly buried methane hydrate in a mud volcano located 24 km offshore southern California in?? 800 m of water. Bivalves, authigenic calcite, and methane hydrate were recovered in a 2.1 m piston core. Aragonite shells of two bivalve species are unusually depleted in 13C (to -91??? ??13C), the most 13C-depleted shells of marine macrofauna yet discovered. Carbon isotopes for both living and dead specimens indicate that they used, in part, carbon derived from anaerobically oxidized methane to construct their shells. The ??13C values are highly variable, but most are within the range -12??? to -91???. This variability may be diagnostic for identifying cold-seep-hydrate systems in the geologic record. Authigenic calcite is abundant in the cores down to ???1.5 m subbottom, the top of the methane hydrate. The calcite is depleted in 13C (??13C = -46??? to -58???), indicating that carbon produced by anaerobically oxidized methane is the main source of the calcite. Methane sources include a geologic hydrocarbon reservoir from Miocene source rocks, and biogenic and thermogenic degradation of organic matter in basin sediments. Oxygen isotopes indicate that most calcite formed out of isotopic equilibrium with ambient bottom water, under the influence of gas hydrate dissociation and strong methane flux. High metal content in the mud volcano sediment indicates leaching of basement rocks by fluid circulating along an underlying fault, which also allows for a high flux of fossil methane. ?? 2006 Geological Society of America.

Geology↗

USGS2006

Determination of the platinum - Group elements (PGE) and gold (Au) in manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with ICP-MS

Platinum group elements (PGE) and Au data in polymetallic oceanic ferromanganese nodule reference samples and crust samples obtained by inductively coupled plasma mass spectrometry (ICP-MS), after separation and pre-concentration by nickel sulfide fire-assay and Te coprecipitation, are presented. By optimizing several critical parameters such as flux composition, matrix matching calibration, etc., best experimental conditions were established to develop a method suitable for routine analysis of manganese nodule samples for PGE and Au. Calibrations were performed using international PGE reference materials, WMG-1 and WMS-1. This improved procedure offers extremely low detection limits in the range of 0.004 to 0.016 ng/g. The results obtained in this study for the reference materials compare well with previously published data wherever available. New PGE data arc also provided on some international manganese nodule reference materials. The analytical methodology described here can be used for the routine analysis of manganese nodule and crust samples in marine geochemical studies.

Indian Journal of Marine Sciences↗

USGS2005

Sub-seafloor acoustic characterization of seamounts near the Ogasawara Fracture Zone in the western Pacific using chirp (3-7 kHz) subbottom profiles

A detailed analysis of chirp (3-7 kHz) subbottom profiles and bathymetry was performed on data collected from seamounts near the Ogasawara Fracture Zone (OFZ) in the western Pacific. The OFZ, which is a 150 km wide rift zone showing 600 km of right-lateral movement in a NW-SE direction, is unique among the fracture zones of the Pacific in that it includes many old seamounts (e.g., Magellan Seamounts and seamounts on Dutton Ridge). Sub-seafloor acoustic echoes on the seamounts are classified into nine specific types based on the nature and continuity of the echoes, subbottom structure, and morphology of the seafloor: (1) distinct echoes (types I-1, I-2, I-3), (2) indistinct echoes (types II-1, II-2, II-3), and (3) hyperbolic echoes (types III-1, III-2, III-3). Type I-2 pelagic sediments, characterized by thin and intermittent coverage, were probably deposited in topographically sheltered areas when bottom currents were strong, whereas type I-1 pelagic sediments accumulated during continuous and widespread sedimentation. Development of seamount flank rift zones in the OFZ may have been influenced by preexisting structures in the transform fracture zone at the time of volcanism, whereas those on Ita Mai Tai seamount in the Pigafetta Basin originated solely by edifice-building processes. Flank rift zones that formed by dike intrusions and eruptions played an important role in mass wasting. Mass-wasting processes included block faulting or block slides around the summit margin, sliding/slumping, debris flows, and turbidites, which may have been triggered by faulting, volcanism, dike injection, and weathering during various stages in the evolution of the seamounts. ?? 2005 Elsevier Ltd. All rights reserved.

Deep-Sea Research Part I: Oceanographic Research P↗

USGS2005

Osmium isotope stratigraphy of a marine ferromanganese crust

Ferromanganese crusts provide records of long term change in ocean circulation and continental weathering. However, calibrating their age prior to 10 Ma has been entirely based on empirical growth rate models using Co concentrations, which have inherently large uncertainties and fail to detect hiatuses and erosional events. We present a new method for dating these crusts by measuring their osmium (Os) isotope record and matching it to the well-known marine Os isotope evolution of the past 80 Ma. The well-characterised crust CD29-2 from the central Pacific, was believed to define a record of paleooceanographic change from 50 Ma. Previous growth rate estimates based on the Co method are consistent with the new Os isotope stratigraphy but the dating was grossly inaccurate due to long hiatuses that are now detectable. The new chronology shows that it in fact started growing prior to 70 Ma in the late Cretaceous and stopped growing or was eroded between 13.5 and 47 Ma. With this new technique it is now possible to exploit the full potential of the oceanographic and climatic records stored in Fe-Mn crusts. ?? 2005 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters↗

USGS2005

Mercury- and silver-rich ferromanganese oxides, southern California Borderland: Deposit model and environmental implications

Mercury- and silver-enriched ferromanganese oxide crusts were recovered at water depths of 1,750 tol,300 m from La Victoria knoll, located about 72 km off the coast of northern Baja California. No other ferromanganese precipitate found so far in the modern ocean basins is similarly enriched in Hg and Ag. The precipitates consist of submetallic gray, brecciated, Mn oxide layers overlain by brown earthy, laminated Fe-Mn oxide crusts. Both oxide types are rich in Hg (to 10 ppm) and Ag (to 5.5 ppm). The Mn-rich layers are composed of ??MnO2, with lesser amounts of 10A?? and 7A?? manganates, whereas the Mn phase in the Fe-Mn crusts is solely ??MnO2. The Fe phase in both layers is X-ray amorphous. Established criteria for distinguishing hydrothermal versus hydrogenetic crusts indicate that the Mn-rich layers are predominantly of low-temperature hydrothermal origin, whereas the Fe-Mn crusts are hydrogenetic, although there is some overlap in the source of chemical components in both types. La Victoria knoll is uplifted continental basement rock with basalt, andesite, and schist cropping out at the surface; the knoll may have an intrusive core. The Hg and Ag were derived from leaching by hydrothermal fluids of organic matter-rich sediments in basins adjacent to La Victoria knoll and, to a lesser extent, from continental basement rocks underlying the knoll and adjacent basins. Both rock types are notably enriched in Ag and Hg. Faults were the main fluid transport pathway, and hydrothermal circulation was driven by high heat flow associated with thinned crust. Other elements derived from the hydrothermal fluids include Tl, Cd, Cr, and Li. The main host for Hg and Ag is FeOOH, although MnO2 likely hosts some of the Ag. Minor sulfide and barite also may contain small amounts of these metals. Possible analogs in the geologic record for this deposit type are found in the Basin and Range province of the western United States and Mexico. The discovery highlights the fact that fluids circulating along faults in the offshore California borderland are transporting potentially toxic metals (Hg, Ag, Tl, As, Cd, Cr, Pb, and Ni) and depositing them on and just below the ocean floor. ?? 2005 Society of Economic Geologists, Inc.

Economic Geology↗

USGS2005

Lagoonal reef accretion and holocene sea-level history from three atolls in the Cook Islands, Central South Pacific

Radiocarbon ages of corals from cores collected at nine drill sites in the lagoons of three atolls (Pukapuka, Rakahanga, Aitutaki, Cook Islands) provide a history of lagoon sedimentation in response to Holocene sea-level rise and stabilization. Holocene lagoonal reefs were established between 8700 and 7800 years B.P. on 130,000-200,000 year-old reef platforms that are presently 7 to 22 m below the floor of the lagoons. Comparison of radiocarbon ages of the deepest corals to published sea-level curves indicate that Holocene reefs colonized these substrates rapidly (<???500 years) after lagoon flooding, in water depths of less than 8 m. Subsequently, reef growth lagged behind sea-level rise until the outer reef rims reached sea level between 5000 and 4000 years B.P. Average vertical sediment accretion rates for the Holocene in the lagoons varied by location (83 ?? 2 to 278 ?? 8 cm/ka) and decreased through the Holocene in six of seven drill holes as the lagoons shallowed and became enclosed by the outer reef. A sample from an emergent (<0.5 m above present mean tide) reef on Rakahanga is 4610 ?? 100 years old, which may indicate a higher middle Holocene relative sea level on Rakahanga. Coral growth in Rakahanga lagoon ceased less than 2000 years ago, but was prolific in the early to middle Holocene. The timing and pattern of Holocene reef development exhibited in the Cook Islands is consistent with other oceanic islands. An assessment of the response of reef development to sea-level change during the Holocene provides a baseline to predict how future sea-level changes may affect the morphology of modern reefs.

Journal of Coastal Research↗

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↗

USGS2004

New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts

The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters. For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific ENd and EHf both decrease with water depth. Similarly, ENd and EHf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable. The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific. Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation. Copyright ?? 2004 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

USGS2004

Cenozoic marine geochemistry of thallium deduced from isotopic studies of ferromanganese crusts and pelagic sediments

Cenozoic records of Tl isotope compositions recorded by ferromanganese (Fe-Mn) crusts have been obtained. Such records are of interest because recent growth surfaces of Fe-Mn crusts display a nearly constant Tl isotope fractionation relative to seawater. The time-series data are complemented by results for bulk samples and leachates of various marine sediments. Oxic pelagic sediments and anoxic marine deposits can be distinguished by their Tl isotope compositions. Both pelagic clays and biogenic oozes are typically characterized by ??205Tl greater than +2.5, whereas anoxic sediments have ??205Tl of less than -1.5 (??205Tl is the deviation of the 205Tl/203Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 104). Leaching experiments indicate that the high ??205Tl values of oxic sediments probably reflect authigenic Fe-Mn oxyhydroxides. Time-resolved Tl isotope compositions were obtained from six Fe-Mn crusts from the Atlantic, Indian, and Pacific oceans and a number of observations indicate that these records were not biased by diagenetic alteration. Over the last 25 Myr, the data do not show isotopic variations that significantly exceed the range of Tl isotope compositions observed for surface layers of Fe-Mn crusts distributed globally (??205 Tl=+12.8??1.2). This indicates that variations in deep-ocean temperature were not recorded by Tl isotopes. The results most likely reflect a constant Tl isotope composition for seawater. The growth layers of three Fe-Mn crusts that are older than 25 Ma show a systematic increase of ??205Tl with decreasing age, from about +6 at 60-50 Ma to about +12 at 25 Ma. These trends are thought to be due to variations in the Tl isotope composition of seawater, which requires that the oceans of the early Cenozoic either had smaller output fluxes or received larger input fluxes of Tl with low ??205Tl. Larger inputs of isotopically light Tl may have been supplied by benthic fluxes from reducing sediments, rivers, and/or volcanic emanations. Alternatively, the Tl isotope trends may reflect the increasing importance of Tl fluxes to altered ocean crust through time. ?? 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

Uptake of elements from seawater by ferromanganese crusts: Solid-phase associations and seawater speciation

Marine Fe-Mn oxyhydroxide crusts form by precipitation of dissolved components from seawater. Three hydrogenetic crust samples (one phosphatized) and two hydrothermal Mn-oxide samples were subjected to a sequential-leaching procedure in order to determine the host phases of 40 elements. Those host-phase associations are discussed with respect to element speciation in seawater. The partitioning of elements between the two major phases, Mn oxide and Fe oxyhydroxide, can in a first-order approximation be explained by a simple sorption model related to the inorganic speciation of the elements in seawater, as has been proposed in earlier models. Free and weakly complexed cations, such as alkali and alkaline earth metals, Mn, Co, Ni, Zn, T1(I), and partly Y, are sorbed preferentially on the negatively charged surface of the MnO2 in hydrogenetic crusts. The driving force is a strong coulombic interaction. All neutral or negatively charged chloro (Cd, Hg, T1), carbonate (Cu, Y, Pb, and U), and hydroxide (Be, Sc, Ti, Fe, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, Bi, Th, and T1(III)) complexes and oxyanions (V, Cr, As, Se, Mo, and W) bind to the slightly positively charged surface of the amorphous FeOOH phase. While coulombic interaction can explain the sorption of the negatively charged species, the binding of neutral species is based on specific chemical interaction. Organic complexation of elements in deep-ocean water seems to be at most of minor importance. Surface oxidation can explain some strong metal associations, e.g. of Co and T1 with the MnO2 and Te with the FeOOH. Sorption reactions initially driven by coulombic forces are often followed by the formation of specific bonds between the adsorbate and the atoms of the oxide surface. Differences in the associations of some metals between the non-phosphatized and phosphatized hydrogenetic crusts and between the hydrogenetic and the hydrothermal samples reflect the different physico-chemical environments of formation and speciations in oxic seawater vs. less-oxic fluids, especially for the redox-sensitive metals such as Mo and V. These environmental-related differences indicate that the methodology of chemical speciation used here in combination with spectroscopic methods may allow for the detection of changes in paleoceanographic conditions recorded during the several tens of millions of years of crust growth. ?? 2003 Elsevier Science B.V. All rights reserved.

Marine Geology↗

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↗