Annotated record of the detailed examination of Mn nodules recovered from the VA04 expedition (R/V Valdivia) in the Pacific Ocean

Twenty-four manganese nodules from the surface of the sea floor and fifteen buried nodules were studied. With three exceptions, the nodules were collected from the area covered by Valdivia Cruise VA 04 some 1200 nautical miles southeast of Hawaii. Age determinations were made using the ionium method. In order to get a true reproduction of the activity distribution in the nodules, they were cut in half and placed for one month on nuclear emulsion plates to determine the alpha-activity of the ionium and its daughter products. Special methods of counting the alpha-tracks resolution to depth intervals of 0.125 mm. For the first time it was possible to resolve zones of rapid growth (impulse growth) with growth rates, s > 50 mm/106 yr and interruptions in growth. With few exceptions the average rate of growth of all nodules was surprisingly uniform at 4-9 mm/10 yr. No growth could be recognized radioactively in the buried nodules. One exceptional nodule has had recent impulse growth and, in the material formed, the ionium is not yet in equilibrium with its daughter products. Individual layers in one nodule from the Indian Ocean could be dated and an average time interval of t = 2600±400 yr was necessary to form one layer. The alternation between iron and manganese-rich parts of the nodules was made visible by colour differences resulting from special treatment of cut surfaces with HCl vapour. The zones of slow growth of one nodule are relatively enriched in iron. Earlier attempts to find paleomagnetic reversals in manganese nodules have been continued. Despite considerable improvement in areal resolution, reversals were not detected in the nodules studied. Comparisons of the surface structure, microstructure in section and the radiometric dating show that there are erosion surfaces and growth surfaces on the outer surfaces of the manganese nodules. The formation of cracks in the nodules was studied in particular. The model of age-dependent nodule shrinkage and cracking surprisingly indicates that the nodules break after exceeding a certain age and/or size. Consequently, the breaking apart of manganese nodules is a continuous process not of catastrophic or discontinuous origin. The microstructure of the nodules exhibits differences in the mechanism of accretion and accretion rate of material, shortly referred to as accretion form. Thus non-directional growth inside the nodules as well as a directional growth may be observed. Those nodules with large accretion forms have grown faster than smaller ones. Consequently, parallel layers indicate slow growth. The upper surfaces of the nodules, protruding into the bottom water appear to be more prone to growth disturbances than the lower surfaces, immersed in the sediment. Features of some nodules show, that as they develop, they neither turned nor rolled. Yet unknown is the mechanism that keeps the nodules at the surface during continuous sedimentation. All in all, the nodules remain the objects of their own distinctive problems. The hope of using them as a kind of history book still seems to be very remote.

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.

Annotated record of the detailed examination of Mn deposits recovered by the Geological Survey of Japan (GSJ) during the 1971-1974 period in the Pacific Ocean

In 1974, the Geological Survey of Japan began its systematic investigation of manganese nodules in the Central Pacific Basin on the new geological research vessel Hakurei Maru. The first cruise (GH 74-5) was carried out over an eastern part area of the Basin (6°-10°30'N, 164°30'-171°30'W), and the authors report here the preliminary results on the occurrence of manganese nodule deposits, paying particular consideration to their relationship to submarine topography and surficial and sub-bottom sedimentary facies. The surveyed area comprises a deep-sea basin at 5,000-5,400 m, defined to the north and east by the chain of seamounts and guyots of the Christmas Ridge. The deep-sea basin is divided roughly into 2 contrasting topographic features. The eastern part is characterised by flattened topography resulting from continuous deposition of turbidities; the meridian and western parts are characterised by gently rolling topography and the existence of a large number of deep-sea hills. Manganese nodules are almost lacking in the former flattened eastern area, whereas they are widely distributed in the latter rolling meridian and western parts. The population density of nodules varies from less than 1 Kg/m² to 26 kg/m² and the higher density is found in the siliceous-calcareous ooze zone of rather small, flat basins surrounded by deep-sea hills. The density is closely related to the thickness of the transparent layer obtained by 3.5 kHz PDR profiling over the whole area. Considering the various data of grab sampling, 3.5 kHz PDR profiling and to a lesser extent of deep-sea television and camera observations, the most promising manganese field in the present area seems to be confined to the north of the western sector of the area.

N2 fixation in eddies of the eastern tropical South Pacific Ocean

Mesoscale eddies play a major role in controlling ocean biogeochemistry. By impacting nutrient availability and water column ventilation, they are of critical importance for oceanic primary production. In the eastern tropical South Pacific Ocean off Peru, where a large and persistent oxygen-deficient zone is present, mesoscale processes have been reported to occur frequently. However, investigations into their biological activity are mostly based on model simulations, and direct measurements of carbon and dinitrogen (N2) fixation are scarce. We examined an open-ocean cyclonic eddy and two anticyclonic mode water eddies: a coastal one and an open-ocean one in the waters off Peru along a section at 16°S in austral summer 2012. Molecular data and bioassay incubations point towards a difference between the active diazotrophic communities present in the cyclonic eddy and the anticyclonic mode water eddies. In the cyclonic eddy, highest rates of N2 fixation were measured in surface waters but no N2 fixation signal was detected at intermediate water depths. In contrast, both anticyclonic mode water eddies showed pronounced maxima in N2 fixation below the euphotic zone as evidenced by rate measurements and geochemical data. N2 fixation and carbon (C) fixation were higher in the young coastal mode water eddy compared to the older offshore mode water eddy. A co-occurrence between N2 fixation and biogenic N2, an indicator for N loss, indicated a link between N loss and N2 fixation in the mode water eddies, which was not observed for the cyclonic eddy. The comparison of two consecutive surveys of the coastal mode water eddy in November 2012 and December 2012 also revealed a reduction in N2 and C fixation at intermediate depths along with a reduction in chlorophyll by half, mirroring an aging effect in this eddy. Our data indicate an important role for anticyclonic mode water eddies in stimulating N2 fixation and thus supplying N offshore.

(Table 3) Age determination of sediment cores from the SW Pacific Ocean

Eight- to ten-point depth profiles (from 1200 to 4800 m water depth) of oxygen and carbon isotopic values derived from benthic foraminifera, averaged over selected times in the past 160 ka, are presented. The data are from 10 sediment cores off eastern New Zealand, mainly North Chatham Rise. This lies under the Deep Western Boundary Current in the Southwest Pacific and is the main point of entry for several water masses into the Pacific Ocean. The benthic isotopic profiles are related to the structure of water masses at present and inferred for the past. These have retained a constant structure of Lower Circumpolar Deep Water-Upper Circumpolar Deep Water/North Pacific Deep Water-Antarctic Intermediate Water with no apparent changes in the depths of water mass boundaries between glacial and interglacial states. Sortable silt particle size data for four cores are also examined to show that the vigour of the inflow to the Pacific, while variable, appears to have remained fairly constant on average. Among the lowest Last Glacial Maximum values of benthic d13C in the world ocean (-1.03 per mil based on Cibicidoides wüllerstorfi) occurs here at ~2200 m. Comparable values occur in the Atlantic sector of the Southern Ocean, while those from the rest of the Pacific are distinctly higher, confirming that the Southern Ocean was the source for the unventilated/nutrient-enriched water seen here. Oxygen and carbon isotopic data are compatible with a glacial cold deep water mass of high salinity, but lower nutrient content (or better ventilated), below ~3500 m depth. This contrasts with the South Atlantic where unventilated/nutrient-enriched water extends all the way to the sea bed. Comparison with previous studies also suggests that the deeper reaches of the Antarctic Circumpolar Current below ~3500 m are not homogeneous all around the Southern Ocean, with the Kerguelen Plateau and/or the Macquarie-Balleny Ridges posing barriers to the eastward spread of the deepest low-d13C water out of the South Atlantic in glacials. These barriers, combined with inferred high density of bottom waters, restricted inter-basin exchange and allow three glacial domains dominated by bottom waters from Weddell Sea, Adelie Coast and Ross Sea to be defined. We suggest that the Ross Sea was the main source of the deep water entering the Pacific below ~3500 m.

(Table 1) Planktonic foraminifera counts and stable oxygen isotope ratios of Pacific Ocean surface sediments

Core-top samples from the eastern tropical Pacific (10°N to 20°S) were used to test whether the ratio between Globorotalia menardii cultrata and Neogloboquadrina dutertrei abundance (Rc/d) and the oxygen isotope composition (?18O) of planktonic foraminifera can be used as proxies for the latitudinal position of the Equatorial Front. Specifically, this study compares the ?18O values of eight species of planktonic foraminifera (Globigerinoides ruber sensu stricto (ss) and sensu lato (sl), Globigerinoides sacculifer, Globigerinoides triloba, Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, Globorotalia menardii menardii, Globorotalia menardii cultrata and Globorotalia tumida) with the seasonal hydrography of the region, and evaluates the application of each species or combination of species for paleoceanographic reconstructions. The results are consistent with sea surface temperature and water column stratification patterns. We found that in samples north of 1°N, the Rc/d values tend to be higher and d18O values of G. ruber, G. sacculifer, G. triloba, P. obliquiloculata, N. dutertrei, and G. menardii cultrata tend to be lower than those from samples located south of 1°N. We suggest that the combined use of Rc/d and the d18O difference between G. ruber and G. tumida or between P. obliquiloculata and G. tumida are the most suitable tools for reconstructing changes in the latitudinal position of the Equatorial Front and changes in the thermal stratification of the upper water column in the eastern tropical Pacific.

(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.

Data on the biogeochemical cycle of methane in the ocean

Geological, mineralogical and microbiological aspects of the methane cycle in water and sediments of different areas in the oceans are under consideration in the monograph. Original and published estimations of formation- and oxidation rates of methane with use of radioisotope and isotopic methods are given. The role of aerobic and anaerobic microbial oxidation of methane in production of organic matter and in formation of authigenic carbonates is considered. Particular attention is paid to processes of methane transformation in areas of its intensive input to the water column from deep-sea hydrothermal sources, mud volcanoes, and cold methane seeps.

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.

Trace element contents in bottom sediments from the North Indian Ocean

Contents and distributions of Cu, Ni, Co, V, Cr, Zn, Pb, Mo, W, and Zr in near-coast and pelagic sediments of the Northern Indian Ocean are under consideration in the paper. Chemical analyses showed enrichment of pelagic clayey radiolarian oozes by Mn, Cu, Ni, Co, Pb, W, and Mo. According to enrichment factors these elements have the following order: Mo> Mn> Cu> Ni> Co> Pb> W. Enrichment of pelagic sediments from the Indian Ocean is mainly determined by the mechanism of the sedimentation process. Enrichment factors of Cu, Ni, Co, W, Mo, and Mn in pelagic sediments of the North Indian Ocean are intermediate between ones in pelagic sediments of the Pacific and Atlantic Oceans.

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.