The San Gregorio Formation in Baja California Sur, a phosphate-enriched sedimentary unit of late Oligocene to early Miocene age, has been analyzed in two areas (La Purisima and San Hilario) for its chemical composition (major oxides, Cu, Cd, Cr, Co, V, and rare-earth elements - REE) and isotopic composition (??18O and ??13C). A detrital and a marine component were determined from major oxides. The detrital component consists of an unaltered volcanic-ash fraction and a terrigenous clay-silt fraction. The marine component, which accumulated initially as biogenic and hydrogenous material, is now present as opal-A, opal-CT, CaCO3, organic matter, and an authigenic phosphate fraction, mostly pelletal and composed of the carbonate-fluorapatite mineral francolite. The minor elements have been partitioned into these components by assuming a constant composition for the two detrital fractions. The composition of the marine component of minor elements can then be interpreted by assuming that the stoichiometry of the original accumulating organic matter was equal to that of modern plankton. The Cu and Cd contents in the marine component of all rocks require that the seawater-derived fractions of these two metals were supplied to the seafloor solely by organic matter. Enrichments of Cr and V at both sites required an additional marine input. On the basis of their geochemistry in the modern ocean, Cr and V could have precipitated, or been adsorbed, onto settling particles from an O2 minimum zone in which the O2 content was low enough to promote denitrification rather than oxygen respiration. An enrichment of the REE, now within the apatite fraction, resulted from their adsorption onto particulates also in the O2 minimum zone and to the dissolution and alteration of biogenic phases (predominantly silica) within the sediment. Co and Fe2O3 show no enrichment above a detrital contribution. The ??18O-values of apatites from the La Purisima site are heavier than those of apatites from the San Hilario site, whereas the ??13C-values show the opposite trend. One possible interpretation of these variations is that ??18O reflects seawater values and ??13C sediment pore water values. This interpretation suggests that upwelling rates and primary productivity within the water column were greater at La Purisima, an interpretation that is corroborated by a greater abundance of apatite measured in outcrop at La Purisima. The Ce anomalies of the phosphate-enriched samples also differ between the two sites, indicating that they also recorded water masses, similar to the ??18O-values. ?? 1991.

Chemical Geology↗

USGS1988

The metal oxide fraction of pelagic sediment in the equatorial North Pacific Ocean: A source of metals in ferromanganese nodules

Pelagic sediment recovered at DOMES Site A in the equatorial North Pacific (151°W, 9° 15′N) consists of a surface homogeneous layer, approximately 10 cm thick, overlying a strongly mottled layer that is lighter in color. The radiolarian composition of both units is Quaternary. In areas where this sediment was only a few centimeters thick, the underlying sediment was early Tertiary. Clay mineralogy and major oxide composition of the two Quaternary sediments are uniform. Their similarity to continental shale suggests that the sediment has a terrigenous source. Clay mineralogy and major oxide composition of the Tertiary sediment also are uniform, although they differ markedly from the Quarternary sediment. In contrast to the major oxides, concentrations of Mn, Co, Cu, and Ni soluble in hydroxylamine hydrochlorideacetic acid are strongly different in the surface and subsurface Quaternary sediment. Mn and Ni exhibit pronounced depletions in the subsurface sediment, Ni slightly more than Mn. Cu is also depleted in the subsurface sediment, but less than Mn. It is also depleted in the subsurface Tertiary sediment, whereas the Mn concentration remains high. Concentration of Co relative to Mn increases into the subsurface Quaternary sediment to a constant Co:Mn ratio of 3 × 10 −2 . The trivalent REE (the REE exclusive of Ce) and Fe exhibit little down-core variation. Distribution of elements in these sediments is closely related to their concentration in associated surface ferromanganese nodules. The nodules are of two distinct types: those from the area where the Quaternary sediment is relatively thick have δ-MnO 2 as the dominant manganese mineral. The ratios of Ni:Mn, Cu:Mn, and Fe:Mn in these nodules approximate the corresponding ratios of the soluble fraction of surface sediment. Todorokite is the dominant mineral of nodules recovered from areas where the Quaternary sediment is thin. Relatively high Cu/Mn, Ni/Mn, and low Fe/Mn ratios of these nodules mirror differences between the soluble fraction of surface and subsurface Quaternary sediment. These compositional trends of sediment and nodules at DOMES Site A reflect a diagenetic origin for the todorokite nodules and a predominantly hydrogenous origin for the δ-MnO 2 nodules.

Geochimica et Cosmochimica Acta↗

USGS1988

Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE P 2 O 5 "> REEP2O5 ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 × 10 −3 (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment.

Marine Geology↗

USGS1987

Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A, northern equatorial Pacific

The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies. The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source.

Geochimica et Cosmochimica Acta↗

USGS1987

The chemistry and mineralogy of haloed burrows in pelagic sediment at DOMES Site A: The equatorial North Pacific

The chemical and mineralogical composition of burrowed sediment, recovered in 66 box cores at latitude 9°25′N and longitude 151°15′W in the equatorial Pacific, demonstrates the important role of infauna in determining the geochemistry of pelagic sediment. Haloed burrows, approximately 3 cm across, were present in many of the cores. Within early Tertiary sediment that was covered by less than 5 cm of surface Quaternary sediment in several cores, the burrows in cross-section consist of three units: (1) a dark yellowish-brown central zone of Quaternary sediment surrounded, by (2) a pale yellowish-orange zone (the halo) of Tertiary sediment, which is surrounded by (3) a metal-oxide precipitate; the enclosing Tertiary sediment is dusky brown. Several elements — Mn, Ni, Cu, Co, Zn, Sb and Ce — have been leached from the light-colored halo, whereas Cr, Cs, Hf, Rb, Sc, Ta, Th, U, the rare earth elements exclusive of Ce, and the major oxides have not been leached. The metal-oxide zone, 1–5 mm thick, contains as much as 16% MnO 2 , as the mineral todorokite. The composition of the todorokite, exclusive of the admixed Tertiary sediment, resembles the composition of the metal deficit of the halo and also the composition of surface ferromanganese nodules that have been interpreted as having a predominantly diagenetic origin. Thus bioturbation contributes not only to the redistribution of metals within pelagic sediment, but also to the accretion of ferromanganese nodules on the sea floor.

Marine Geology↗

USGS1987

Distribution of ferromanganese nodules in the Pacific Ocean.

The occurrence and distribution of deep-ocean ferromanganese nodules are related to the lithology of pelagic surface-sediment, sediment accumulation rates, sea-floor bathymetry, and benthic circulation. Nodules often occur in association with both biosiliceous and pelagic clay, and less often with calcareous sediment. Factors which influence the rather complex patterns of sediment lithology and accumulation rates include the supply of material to the sea-floor and secondary processes in the deep ocean which alter or redistribute that supply. The supply is largely controlled by: 1) proximity to a source of alumino-silicate material and 2) primary biological productivity in the photic zone of the ocean. Primary productivity controls the 'rain' to the sea-floor of biogenic detritus, which consists mostly of siliceous and calcareous tests of planktonic organisms but also contains smaller proportions of phosphatic material and organic matter. The high accumulation rate (5 mm/1000 yr) of sediment along the equator is a direct result of high productivity in this region of the Pacific. Secondary processes include the dissolution of particulate organic matter at depth in the ocean, notably CaCO3, and the redistribution of sedimentary particles by deep-ocean currents. -J.M.H.

Chemie der Erde↗

USGS1985

Chemistry of pelagic sediment and associated ferromanganese nodules; DOMES Site A, Equatorial North Pacific

Explore the source record for details and available documents.

Open-File Report↗

USGS1984

Ferromanganese nodules from MANOP Sites H, S, and R-Control of mineralogical and chemical composition by multiple accretionary processes

The chemical composition of ferromanganese nodules from the three nodule-bearing MANOP sites in the Pacific can be accounted for in a qualitative way by variable contributions of distinct accretionary processes. These accretionary modes are: 1. (1) hydrogenous, i.e ., direct precipitation or accumulation of colloidal metal oxides in seawater, 2. (2) oxic diagenesis which refers to a variety of ferromanganese accretion processes occurring in oxic sediments; and 3. (3) suboxic diagenesis which results from reduction of Mn +4 by oxidation of organic matter in the sediments. Geochemical evidence suggests processes (1) and (2) occur at all three MANOP nodule-bearing sites, and process (3) occurs only at the hemipelagic site, H, which underlies the relatively productive waters of the eastern tropical Pacific. A normative model quantitatively accounts for the variability observed in nearly all elements. Zn and Na, however, are not well explained by the three end-member model, and we suggest that an additional accretionary process results in greater variability in the abundances of these elements. Variable contributions from the three accretionary processes result in distinct top-bottom compositional differences at the three sites. Nodule tops from H are enriched in Ni, Cu, and Zn, instead of the more typical enrichments of these elements in nodule bottoms. In addition, elemental correlations typical of most pelagic nodules are reversed at site H. The three accretionary processes result in distinct mineralogies. Hydrogenous precipitation produces δMnO 2 . Oxic diagenesis, however, produces Cu-Ni-rich todorokite, and suboxic diagenesis results in an unstable todorokite which transforms to a 7 Å phase (“birnessite”) upon dehydration. The presence of Cu and Ni as charge-balancing cations influence the stability of the todorokite structure. In the bottoms of H nodules, which accrete dominantly by suboxic diagenesis, Na + and possibly Mn +2 provide much of the charge balance for the todorokite structure. Limited growth rate data for H nodules suggest suboxic accretion is the fastest of the three processes, with rates at least 200 mm/10 6 yr. Oxic accretion is probably 10 times slower and hydrogenous 100 times slower. Since these rates predict more suboxic component in bulk nodules than is calculated by the normative analysis, we propose that suboxic accretion is a non-steady-state process. Variations in surface water productivity cause pulses of particulate flux to the sea floor which result in transient Mn reduction in the surface sediments and reprecipitation on nodule surfaces.

Geochimica et Cosmochimica Acta↗

USGS1984

Oxidation state of marine manganese nodules

Analyses of the bulk oxidation state of marine manganese nodules indicates that more than 98% of the Mn in deep ocean nodules is present as Mn(IV). The samples were collected from three quite different areas: the hemipelagic environment of the Guatemala Basin, the pelagic area of the North Pacific, and seamounts in the central Pacific. Results of the study suggest that todorokite in marine nodules is fully oxidized and has the following stoichiometry: (K, Na, Ca, Ba) .33 (Mg, Cu, Ni) .76 Mn 5 O 22 (H 2 O) 3.2 .

Geochimica et Cosmochimica Acta↗

USGS1984

Geochemistry of ferromanganese nodules from DOMES site a, Northern Equatorial Pacific: Multiple diagenetic metal sources in the deep sea

The major and minor element composition of ferromanganese nodules from DOMES Site A has been determined by X-ray fluorescence methods. Three phases appear to control the bulk compositions: Mn and Fe oxyhydroxides and aluminosilicates. Relatively wide compositional variations are evident throughout the area. Nodules with high Mn/Fe ratios, high Cu, Mg, Mo, Ni and Zn concentrations and high todorokite/δ-MnO 2 ratios have granular surface textures and are confined to an east-west trending depression with thin Quaternary sediment cover. Nodules with low Mn/Fe ratios, high concentrations of As, Ca, Ce, Co, La, P, Sr, Ti, V, Y and Zr and low todorokite/δ-MnO 2 ratios have smooth surfaces and are confined to shallower areas with relatively thick Quaternary sediment to the north and south of the depression. All nodules in the area have compositions which are influenced by diagenesis, but those with the most marked diagenetic signature (high Mn/Fe and Cu/Ni ratios, low Ce/La ratios and more todorokite) are found in areas of very slow or non-existent sedimentation; many of these nodules are actually in contact with outcropping Tertiary sediment. This paradox may be resolved by postulating, by analogy with some shallow-water occurrences, that the nodules accrete from bottom waters which have enhanced particulate and dissolved metal contents derived from diagenetic reaction in areas remote from the site of nodule formation. The metals are supplied in a bottom flow (probably Antarctic Bottom Water) which also erodes, or prevents modern sedimentation in, the depression. Nodules on the flanks of the depression are not evidently affected by this flow and derive at least pan of their constituent metals from diagenetic reaction in the underlying Quaternary sediment. Apparently, abyssal diagenetic nodules can have an immediate and a remote diagenetic metal source. Metal fluxes derived from pore water dissolved metal gradients may not be relevant to particular accreting nodules if a significant fraction of their metals is derived from outside the area in which they form.

Geochimica et Cosmochimica Acta↗

USGS1984

Observations on Cretaceous abyssal hills in the northeast Pacific

An abyssal hills area of 50 × 60 km in the northeast Pacific was studied using bottom transponder navigation, closely spaced survey lines, and long-traverse oblique photography. The block-faulted north—south hills are bounded by scarps, commonly with 40° slopes. On these steep scarps sedimentation is inhibited and pillow basalts often crop out. An ash layer of high acoustic reflectivity at about 7 m subbottom depth blankets the area. This ash occurs in multiple beds altered to phillipsite and is highly consolidated. A 24 m.y. age for the ash is based on ichthyolith dates from samples in the overlying sediments. Acoustically transparent Neogene sediments above the ash are thickest in trough bottoms and are absent or thin on steep slopes. These Neogene sediments are composed of pale-brown pelagic clays of illite, quartz, smectite, chlorite and kaolinite. Dark-brown pelagic clays, rich in smectite and amorphous iron oxides, underlie the Neogene surficial sediments. Manganese nodules cover the bottom in varying percentages. The nodules are most abundant near basement outcrops and where the subbottom ash layer is absent.

Marine Geology↗

USGS1981

Fluxes of metals to a manganese nodule: Radiochemical, chemical, structural, and mineralogical studies

Fluxes of metals to the top and bottom surfaces of a manganese nodule were determined by combining radiochemical ( 230 Th, 231 Pa, 232 Th, 238 U, 234 U) and detailed chemical data. The top of the nodule had been growing in its collected orientation at 4.7 mm Myr −1 for at least 0.5 Myr and accreting Mn at 200 μg cm −2 kyr −1 . The bottom of the nodule had been growing in its collected orientation at about 12 mm Myr −1 for at least 0.3 Myr and accreting Mn at about 700 μg cm −2 yr −1 . Although the top of the nodule was enriched in iron relative to the bottom, the nodule had been accreting Fe 50% faster on the bottom. 232 Th was also accumulating more rapidly in the bottom despite a 20-fold enrichment of 230 Th on the top. The distribution of alpha-emitting nuclides calculated from detailed radiochemical measurements matched closely the pattern revealed by 109-day exposures of alpha-sensitive film to the nodule. However, the shape and slope of the total alpha profile with depth into the nodule was affected strongly by 226 Ra and 222 Rn migrations making the alpha-track technique alone an inadequate method of measuring nodule growth rates. Diffusion of radium in the nodule may have been affected by diagenetic reactions which produce barite, phillipsite and todorokite within 1 mm of the nodule surface; however, our sampling interval was too broad to document the effect. We have not been able to resolve the importance of nodule diagenesis on the gross chemistry of the nodule.

Earth and Planetary Science Letters↗

USGS1981

The aluminosilicate fraction of North Pacific manganese nodules

Nine nodules collected from throughout the deep North Pacific were analyzed for their mineralogy and major-element composition before and after leaching with Chester-Hughes solution. Data indicate that the mineral phillipsite accounts for the major part (> 75%) of the aluminosilicate fraction of all nodules. It is suggested that formation of phillipsite takes place on growing nodule surfaces coupled with the oxidation of absorbed manganous ion. All the nodules could be described as ternary mixtures of amorphous iron fraction (Fe-Ti-P), manganese oxide fraction (Mn-Mg Cu-Ni), and phillipsite fraction (Al-Si-K-Na), these fractions accounting for 96% of the variability of the chemical composition.

Geochimica et Cosmochimica Acta↗

USGS1981

Mineralogy and composition of concentric layers within a manganese nodule from the North Pacific Ocean

The minor-element composition of concentric layers within a single ferromanganese nodule from the eastern North Pacific exhibits strong correlations with Fe and Mn contents but appears to be independent of pronounced mineralogic variations. On the basis of these correlations, the elemental composition of individual layers apparently is controlled by the relative contribution of two sources: seawater, and interstitial water of associated sediment. In contrast, the mineralogy of the nodule, consisting of birnessite in the outer few layers and todorokite in the inner layers, is considered to be a function of nodule diagenesis.

Marine Geology↗