Analysis of manganese deposits from the Pacific Ocean

Sea floor dredging by the H.M.S. Challenger, the U.S.S. Albatross, the U.S.S. EPC(R) 857, and vessels of the Scripps Institution of Oceanography shows that extensive deposits of manganese nodules are on the deep sea floor and that crusts of manganese dioxide cover many seamounts. Sea floor photography reveals that in some places these crusts are quite continuous and the nodules are closely packed. These crusts and nodules are fully oxidized and hydrated mixtures of man¬ganese and iron plus earthy impurities. Also, relatively high concen¬trations of the trace elements nickel, copper, and cobalt are present.

(Table 1, page 1376) Chemical analyses of manganese nodules and crusts from the Pacific Ocean

A compilation of chemical analyses of Pacific Ocean nodules using an x-ray fluorescence technique. The equipment used was a General Electric XRD-5 with a tungsten tube. Lithium fluoride was used as the diffraction element in assaying for all elements above calcium in the atomic table and EDDT was used in conjunction with a helium path for all elements with an atomic number less than calcium. Flow counters were used in conjunction with a pulse height analyzer to eliminate x-ray lines of different but integral orders in gathering count data. The stability of the equipment was found to be excellent by the author. The equipment was calibrated by the use of standard ores made from pure oxide forms of the elements in the nodules and carefully mixed in proportion to the amounts of these elements generally found in the manganese nodules. Chemically analyzed standards of the nodules themselves were also used. As a final check, a known amount of the element in question was added to selected samples of the nodules and careful counts were taken on these samples before and after the addition of the extra amount of the element. The method involved the determination and subsequent use of absorption and activation factors for the lines of the various elements. All the absorption and activation factors were carefully determined using the standard ores. The chemically analyzed samples of the nodules by these methods yielded an accuracy to at least three significant figures.

(Table S1) Calcium isotope ratios of Pacific Ocean sediments

Multiple lines of evidence have shown that the isotopic composition and concentration of calcium in seawater have changed over the past 28 million years. A high-resolution, continuous seawater calcium isotope ratio curve from marine (pelagic) barite reveals distinct features in the evolution of the seawater calcium isotopic ratio suggesting changes in seawater calcium concentrations. The most pronounced increase in the d44/40Ca value of seawater (of 0.3 per mil) occurred over roughly 4 million years following a period of low values around 13 million years ago. The major change in marine calcium corresponds to a climatic transition and global change in the carbon cycle and suggests a reorganization of the global biogeochemical system.

Radiogenic Hf isotopic composition of continental eolian dust in Pacific Ocean sediments

The inorganic silicate fraction extracted from bulk pelagic sediments from the North Pacific Ocean is eolian dust. It monitors the composition of continental crust exposed to erosion in Asia. 176Lu/177Hf ratios of modern dust are subchondritic between 0.011 and 0.016 but slightly elevated with respect to immature sediments. Modern dust samples display a large range in Hf isotopic composition (IC), -4.70 < epsilon-Hf < +16.45, which encompasses that observed for the time series of DSDP cores 885/886 and piston core LL44-GPC3 extending back to the late Cretaceous. Hafnium and neodymium isotopic results are consistent with a dominantly binary mixture of dust contributed from island arc volcanic material and dust from central Asia. The Hf-Nd isotopic correlation for all modern dust samples, epsilon-Hf= =0.78 epsilon-Nd = +5.66 (n =22, R**2 =0.79), is flatter than those reported so far for terrestrial reservoirs. Moreover, the variability in epsilon-Hf of Asian dust exceeds that predicted on the basis of corresponding epsilon-Nd values (34.76 epsilon-Hf < +2.5; -10.96< epsilon-Nd <-10.1). This is attributed to: (1) the fixing of an important unradiogenic fraction of Hf in zircons, balanced by radiogenic Hf that is mobile in the erosional cycle, (2) the elevated Lu/Hf ratio in chemical sediments which, given time, results in a Hf signature that is radiogenic compared with Hf expected from its corresponding Nd isotopic components, and (3) the possibility that diagenetic resetting of marine sediments may incorporate a significant radiogenic Hf component into diagenetically grown minerals such as illite. Together, these processes may explain the variability and more radiogenic character of Hf isotopes when compared to the Nd isotopic signatures of Asian dust. The Hf-Nd isotope time series of eolian dust are consistent with the results of modern dust except two samples that have extremely radiogenic Hf for their Nd (epsilon-Hf =+8.6 and +10.3, epsilon-Nd =39.5 and 39.8). These data may point to a source contribution of dust unresolved by Nd and Pb isotopes. The Hf IC of eolian dust input to the oceans may be more variable and more radiogenic than previously anticipated. The Hf signature of Pacific seawater, however, has varied little over the past 20 Myr, especially across the drastic increase of eolian dust flux from Asia around 3.5 Ma. Therefore, continental contributions to seawater Hf appear to be riverine rather than eolian. Current predictions regarding the relative proportions of source components to seawater Hf must account for the presence of a variable and radiogenic continental component. Data on the IC and flux of river-dissolved Hf to the oceans are urgently required to better estimate contributions to seawater Hf. This then would permit the use of Hf isotopes as a monitor of past changes in erosion.

(Appendix B) Dinoflagellate cysts in Southeast Pacific Ocean surface sediments

orty-eight surface sediment samples from the southeast (SE) Pacific (25-53°S) are investigated for the determination of the spatial distribution of organic-walled dinoflagellate cysts along the western South American continental margin. Fifty-five different taxa are recorded and reflect oceanic or coastal assemblages. The oceanic assemblages are characterised by low cyst concentrations and the dominance of autotrophs, while the coastal assemblages generally contain a higher number of cysts, which are mainly produced by heterotrophic species. Highest cyst concentrations are observed in the active upwelling system offshore Concepción (35-37°S). Brigantedinium spp., Echinidinium aculeatum, Echinidinium granulatum/delicatum and cysts of Protoperidinium americanum dominate assemblages related to upwelling. Echinidinium aculeatum appears to be the best indicator for the presence of all year round active upwelling cells. Other protoperidinioid cysts may also occur in high relative abundances in coastal regions outside active upwelling systems, if the availability of nutrients, co-responsible for the presence/absence of their main food sources such as diatoms and other protists, is sufficient. The importance of nutrient availability as a determining environmental variable influencing cyst signals on a regional scale (SE Pacific) is demonstrated through statistical analyses of the data. Because of the importance of nutrients, uncertainties about the outcomes of quantitative sea-surface temperature (SST) reconstructions (Modern Analogue Technique) based on dinoflagellate cysts may arise, since no interaction between different hydrographical variables is considered in this approach. The combination of the SE Pacific surface sample dataset with other published cyst data from the Southern Hemisphere resulted in a database which includes 350 samples: the 'SH350 database'. This database is used to test the accuracy of the quantitative reconstructions by calculating and comparing the estimated versus observed values for each site. An attempt to perform quantitative SST reconstructions on the last 25 cal ka of site ODP1233 (41°S; 74°27'W) is made and again stresses the importance of other environmental variables such as nutrient availability in determining the dinoflagellate cyst assemblages.

(Table 2, Page 252) Average chemical composition of 11 manganese nodules and crust from the Pacific Ocean

The ability of the hydrated oxides of manganese and iron to adsorb ions from solution (scavenging) is considered in relation to some problems in marine geology, chemistry, and biology. In the ferruginous sediments of the Pacific Ocean, iron oxides are accompanied by titanium, cobalt, and zirconium in amounts proportional to the iron content. Similarly, copper and nickel are linearly related to the manganese content. These observations are explained on the basis of scavenging. An electrochemical theory for the formation of manganese nodules is presented. Marine sediments are classified on the basis of the geosphere in which the solid phases originate. The distribution of certain ionic species in sea water between the solid and aqueous phases is considered on the basis of scavenging and co-ordination compound theory. The concentration of minor elements by members of the marine biosphere is explained either by the direct uptake of the element or by the uptake of iron or manganese oxides with the accompanying scavenged element.

Annotated record of the detailed examination of Mn deposits from the MUKLUK expedition in the North-East Pacific Ocean

The cores and dredges described are taken during the MUKLUK expedition of the R/V Spencer Baird in July-August 1957 by the Scripps Institute of Oceanography. A total of 31 cores and dredges were recovered and are available at Scripps Institute of Oceanography for sampling and study.

Grain size and chemical composition of the surface sediment layer from the Pacific Ocean

The book is devoted to results of studies of Pacific sediment composition, regularities of their distribution and processes of sedimentation in the Pacific Ocean. Materials obtained by Soviet expeditions are the main part of the book.

Particle flux at mooring sites in the Pacific Ocean (Table 1)

In order to understand the vertical transport of particulate matter, suspended and settling particles were collected along a meridional transect between 46°N and 35°S and an equatorial longitudinal transect between 135°E and 175°E in the Pacific. The low COrganic/N atomic ratios (<8.2) of suspended particulate organic matter (OM) and good correlation between particulate organic carbon (OC) and chlorophyll-a confirmed that the suspended particulate OM in the surface water was mainly produced by phytoplankton. Only 0.1-3.2% of primary production was transported to 1.3 km water depth in the boreal central Pacific. All data on settling particles (excluding deep trap data) showed strongly positive correlation between total mass and OM fluxes with high correlation factor of 0.93. Biogenic opal-producing plankton, mainly diatoms were responsible for most of the vertical transport of particulate OM in association with higher COrganic/CCarbonate ratios in the subarctic and equatorial hemipelagic regions in the Pacific. This vertical transport of settling particles potentially works as a sink of CO2. In the transition zone during the May 1993, large difference between PCO2 (<300 µatm) in the surface water and pCO2 (340 µatm) in the atmosphere was actually due to enhanced particulate OM flux. Since the deep water of the Pacific is enriched in CO2 and nutrients, upwelled seawater may tend to release CO2 to the atmosphere. However, higher production of particulate matter could reduce the partial pressure of CO2 in the surface water. Also terrestrial nutrients' inputs in the western equatorial Pacific have potential for the reduction of CO2 in the surface water.

Biogenic components, major, trace and rare earth elements of equatorial Pacific Ocean surface sediments (Table 1)

We have analyzed the major, trace, and rare earth element composition of surface sediments collected from a transect across the Equator at 135°W longitude in the Pacific Ocean. Comparing the behavior of this suite of elements to the CaCO3, opal, and Corg fluxes (which record sharp maxima at the Equator, previously documented at the same sampling stations) enables us to assess the relative significance of the various pathways by which trace elements are transported to the equatorial Pacific seafloor. The 1. (1) high biogenic source at the Equator, associated with equatorial divergence of surface water and upwelling of nutrient-rich water, and 2. (2) high aluminosilicate flux at 4°N, associated with increased terrigenous input from elevated rainfall at the Intertropical Convergence Zone (ITCZ) of the tradewinds, are the two most important fluxes with which elemental transport is affiliated. The biogenic flux at the Equator transports Ca and Sr structurally bound to carbonate tests and Mn primarily as an adsorbed component. Trace elements such as Cr, As, Pb, and the REEs are also influenced by the biogenic flux at the Equator, although this affiliation is not regionally dominant. Normative calculations suggest that extremely large fluxes of Ba and P at the Equator are carried by only small proportions of barite and apatite phases. The high terrigenous flux at the ITCZ has a profound effect on chemical transport to the seafloor, with elemental fluxes increasing tremendously and in parallel with Ti. Normative calculations, however, indicate that these fluxes are far in excess of what can be supplied by lattice-bound terrigenous phases. The accumulation of Ba is greater than is affiliated with biogenic transport at the Equator, while the P flux at the ITCZ is only 10% less than at the Equator. This challenges the common view that Ba and P are essentially exclusively associated with biogenic fluxes. Many other elements (including Mn, Pb, As, and REEs) also record greater accumulation beneath the ITCZ than at the Equator. Thus, adsorptive scavenging by terrigenous paniculate matter, or phases intimately associated with them, appears to be an extremely important process regulating elemental transport to the equatorial Pacific seafloor. These findings emphasize the role of vertical transport to the sediment, and provide additional constraints on the paleochemical use of trace elements to track biogenic and terrigenous fluxes.

(Table 2) Relative contents of clay minerals in aeolian pelagic clays from the Pacific Ocean

For determining importance, composition, and history of aerosol material accumulation in formation of pelagic clays a study with use of light microscopy and scanning electron microscopy, X-ray diffractometry, and chemical methods has been carried out.

(Plate 3) Manganese nodules and deep-sea sediment core from Pacific Ocean

A synoptic review of the studies of well-known occurrences of palagonite tuffs is presented. Included are palagonite tuffs from Iceland, and pillow-lava palagonite complexes from Columbia River basalts and from the central Oregon coast. Additional petrologic and x-ray defraction data for selected samples are presented. Petrologic evidence shows that basaltic glass of aqueous tuffs and breccias consists of sideromelane, which is susceptible to palagonitization. It is shown that palagonitization is a selective alteration process, involving hydration, oxidation and zeolitization. Some of the manganese nodules dredged from the Pacific Ocean floor contain nucleus of palagonite-tuff breccias or of zeolite. A brief megascopic and microscopic description of nodules from the south Pacific, the Mendocino ridge and the 'Horizon' Nodule from the north Pacific is presented. Petrographic studies of palagonite-tuff breccias of manganese nodules and other palagonites suggest that migration and segregation of metallic elements occur during and subsequent to palagonitization. During the palagonitization of sideromelane, nearly 30 percent of sea water is absorbed. The hydration of sideromelane is also accompanied by oxidation of iron and other elements. These oxides may be released either in colloidal form or in true solution and tend to precipitate first from the unstable palagonite.

(Table 1) Iron and manganese speciations in surface layer bottom sediments of the Pacific Ocean

Distribution of iron and manganese speciations in ocean sediments of a section from the coast of Japan to the open Pacific Ocean is under consideration. Determinations of total iron, as well as of reactive iron contents and of total manganese, as well as of Mn4+ contents have been done. Significant increase of total Fe content in sediments from the coast to the pelagic zone occurs without noticeable increase in reactive Fe content. Presence of layers of volcanic and terrigenous coarse clastic material in clayey sediments results to sharp change in iron content. Manganese content increases from near coastal to pelagic sediments more than 10 times; oxidation degree of sediments also increases. There are three types of bottom sediments different by contents of iron and manganese forms: reduced, oxidized (red clay), and transitional. Content of total Fe is almost does not change with depth in sediments, content of reactive Fe increases in reduced sediments, and decreases in oxidized ones. Manganese content in red clay mass increases several times.

Abundance and biomass of benthic foraminifera in bottom sediments from the Sea of Okhotsk and the Pacific Ocean

A study of distribution of live individuals of benthic foraminifera in sediments of the Sea of Okhotsk and of the Northwestern Basin of the Pacific Ocean shows that they can be present in sediments up to depth of 30 cm and probably can live there for long periods, sometimes forming high concentrations. Living individuals in the subsurface layer often account for more than 50% of total biomass, which varies from 1 to 21 g/m**2 in different morphological structures. The largest biomass values are attained in underwater rises embedded in relatively warm, oxygen-saturated Pacific waters. Minimum total biomass concentrations occur in deep-water depressions where stagnation phenomena are observed. Foraminifera biomass everywhere decreases gradually with increasing depth from the surface of sediments regardless of relief, depth, and nature of sediments.