Stable oxygen isotope record and Mg/Ca ratios at the Mid-Pleistocene Climate Transition, ODP Site 181-1123

Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the Mid-Pleistocene Transition (MPT), when the dominant periodicity of climate cycles changed from 41,000 to 100,000 years in the absence of significant change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume at 900 ka. We see no evidence of a pattern of gradual cooling but near-freezing temperatures occur at every glacial maximum.

Geochemistry of Fe-Mn crusts in sediments of the Central Indian Ridge

Layered Fe-Mn crusts from the off-axis region of the first segment of the Central Indian Ridge north of the Rodrigues Triple Junction were studied geochemically and mineralogically. Vernadite (delta-MnO2) is the main mineral oxide phase. 230Thxs and Co concentrations suggest high growth rates of up to 29 mm/Myr and a maximum age of the basal crust layer of 1 Ma. Whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation, Co, Pb, Ni and Ti concentrations are strikingly lower. Concentrations and distribution of the strictly trivalent rare-earths and yttrium (REY) are typical of hydrogenetic ferromanganese oxide precipitates, but in marked contrast, the crusts are characterized by negative CeSN (shale normalized) anomalies and (Ce/Pr)SN ratios less than unity. Profiles through the crusts reveal only minor variations of the REY distribution and (Ce/Pr)SN ratios range from 0.45 to 0.68 (compared to ratios of up to 2 for typical hydrogenetic crusts from the Central Indian Basin). The apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent REY the adsorption-desorption equilibrium has been reached. Positive Ce anomalies in the partition coefficient patterns reveal preferential uptake of Ce, but to a lesser extent than in normal hydrogenetic crusts. A new parameter (excess Ce, Cexs) to quantify the degree of decoupling of Ce from REY(III) is established on the basis of partition coefficients. Cexs/Cebulk ratios suggest that the CIR crusts formed by precipitation of Fe-Mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of Ce results from the same oxidative sorption process. The growth rates, calculated with 230Thxs data as well as with the Co formula, are inversely related to Cexs.

(Table 1) Trace element/Ca ratios of Orbulina universa shells from late Neogene Mediterranean samples

A Mediterranean composite sedimentary record was analyzed for Ba/Ca ratios on carbonate shells of Orbulina universa planktonic foraminifer (Ba/Ca)carb providing the opportunity to study and assess the extent of freshwater inputs on the basin and possible impacts on its dynamics during the Tortonian to Recent period. A number of scanning electron microscope analyses and auxiliary trace element measurements (Mn, Sr, and Mg), obtained from the same samples, exclude important diagenetic effects on the studied biogenic carbonates and corroborate the reliability of (Ba/Ca)carb ratios in foraminifera calcite as indicators of seawater source components during the studied interval. A long-term trend with (Ba/Ca)carb values shifting from ~7 to 3 µmol/mol from the base of the Tortonian to the top of the Messinian is observed. The interval of the late Messinian salinity crisis, where biogenic carbonates are missing or strongly diagenized, represents a crucial passage not monitored in our record. At the base of the Pliocene, up to about 4.7 Ma, the (Ba/Ca)carb record shows a decreasing trend from ~4 µmol/mol stabilizing itself to an about constant value of 0.9 ± 0.3 µmol/mol for the whole Plio-Pleistocene interval. These results suggest a dramatic change in the continental runoff values, up to ~3-16 times higher during part of the late Neogene (Tortonian-early Pliocene), with a possible profound modification in the physical dynamics of the Mediterranean basin. First-order mass balance equations used to estimate barium and salinity budgets in the Mediterranean Sea during the late Miocene-early Pliocene interval support the hypothesis of an active connection of the basin with the Paratethys region and of a definitive restriction at the base of the Pliocene after about 0.7 Ma from the well-known Messinian Lagomare phase. They also open intriguing scenarios on possible circulation shifts during the Neogene.

Sable oxygen isotope and Mg/Ca ratios of planktonic foraminifera from DSDP Hole 31-292

This study presents new evidence of when and how the Western Pacific Warm Pool (WPWP) was established in its present form. We analyzed planktic foraminifera, oxygen isotopes, and Mg/Ca ratios in upper Miocene through Pleistocene sediments collected at Deep Sea Drilling Program (DSDP) Site 292. These data were then compared with those reported from Ocean Drilling Program (ODP) Site 806. Both drilling sites are located in the western Pacific Ocean. DSDP Site 292 is located in the northern margin of the modern WPWP and ODP Site 806 near the center of the WPWP. Three stages of development in surface-water conditions are identified in the region using planktic foraminferal data. During the initial stage, from 8.5 to 4.4 Ma, Site 806 was overlain by warm surface water but Site 292 was not, as indicated by the differences in faunal compositions and sea-surface temperature (SST) between the two sites. In addition, the vertical thermal gradient at Site 292 was weak during this period, as indicated by the small differences in the delta18O values between Globigerinoides sacculifer and Pulleniatina spp. During stage two, from 4.4 to 3.6 Ma, the SST at Site 292 rapidly increased to 27 °C, but the vertical thermal gradient had not yet be strengthened, as shown by Mg/Ca ratios and the presence of both mixed-layer dwellers and thermocline dwellers. Finally, a warm mixed layer with a high SST ca. 28 °C and a strong vertical thermal gradient were established at Site 292 by 3.6 Ma. This event is marked by the dominance of mixed-layer dwellers, a high and stable SST, and a larger differences in the delta18O values between G. sacculifer and Pulleniatina spp. Thus, evidence of surface-water evolution in the western Pacific suggests that Site 292 came under the influence of the WPWP at 3.6 Ma. The northward expansion of the WPWP from 4.4 to 3.6 Ma and the establishment of the modern WPWP by 3.6 Ma appear to be closely related to the closure of the Indonesian and Central American seaways.

Composition of Fe-Mn minerals from island arcs of the West Pacific

This paper presents materials on the chemical and mineralogical composition of Fe-Mn mineralization in island arcs (Kuril, Nampo, Mariana, New Britain, New Hebrides, and Kermadec) in the western part of the Pacific Ocean. The mineralization was proved to be of hydrothermal and/or hydrogenic genesis. The former is produced by hydrothermal Fe and Mn oxi-hydroxides that cement volcanic-terrigenous material in sediments. Some Fe oxyhydroxides can be derived via the halmyrolysis of volcaniclastic material. Crusts of this stage are characterized by fairly low concentrations of trace and rare elements, and their REE composition is inherited from the volcanic-terrigenous material. The minerals of the Mn oxyhydroxides are todorokite and "Ca-birnessite". The Mn/Fe ratio increases away from the discharge sites of the hydrothermal solutions. The hydrogenic Fe-Mn crusts are characterized by high concentrations of trace and minor elements of both the Mn group (Co, Ni, Tl, and Mo) and the Fe group (REE, Y, and Th). The hydrogenic crusts consist of Fe-vernadite and Mn-feroxyhyte. Some of the hydrothermal crusts originally had a hydrothermal genesis. The first data were obtained on crust B30-72-10 from the Macauley Seamount in the Kermadec island arc, which contained anomalously high concentrations of Co (2587 ppm) and other Mn-related trace elements in the absence of hydrogeneous Fe oxyhydroxides.

Benthic foraminiferal Cd/Ca and isotope record from the South Atlantic

A depth transect of cores from 1268 to 3909 m water depth in the western South Atlantic are ideally situated to monitor the interocean exchange of deep water and variations in the relative strength of northern and southern sources of deep water production. Benthic foraminiferal Cd/Ca and d13C data suggest that Glacial North Atlantic Intermediate Water (GNAIW) extended at least as far south as 28°S in the western South Atlantic. The core of nutrient-depleted water was situated at ~1500 m, above and below water masses with higher nutrient concentrations. When examined in conjunction with published paired Cd/Ca and d13C from intermediate depth cores from other basins, it appears that the extent of GNAIW influence on the intermediate waters of the world's oceans was less than suggested previously. Differentiating among possible pathways for the glacial deep ocean (>3 km) requires a better understanding of the controls on Cd/Ca and d13C values of benthic foraminifera.

Fe-Mn nodules and host sediments from the Gulf of Finland

Distributions of major and trace elements in ferromanganese nodules, which are buried or exposed on the sea floor and in host sediments, were studied in ten concretion/sediment pairs by various physical and chemical methods. It was established that, in addition to Fe and Mn, a limited number of major and trace elements (P, Ca, Sr, Ba, Mo, Co, Zn, Ni, As, Pb, Sb, Tl, U, W, Y, and Ga) is accumulated with variable degree of intensity (relative to sediments) in the nodules. The maximal content of Mn in the nodules is 100 times higher than in the host sediments, whereas for all other elements listed above these ratios vary from more than one to 10-20. Manganese and, to a lesser extent, Ba and Sr are concentrated in the buried concretions. Other elements are primarily concentrated in concretions exposed on the sea floor. The occurrence mode of the concretions and compositional data on interstitial water suggest that metals in the concretions derive from seawater and suspended particulates, in addition to sediments. Burial of concretions in the sediment pile is accompanied by alteration of their composition, accumulation of Mn (relative to Fe), and loss of several associated metals.

Composition of Mn-oxide crusts from the south-west Pacific island arc

Hydrothermal deposits of a wide variety of types are being found with increasing frequency on or near actively spreading mid-ocean ridges. However, they also have a potential to occur in other submarine volcanic settings, including island arcs. To follow up indications of mineralization associated with submarine hydrothermal activity in the south-west Pacific island arc, a joint New Zealand Oceanographic Institute/Imperial College research cruise was mounted in May 1981 aboard the RV Tangaroa. During this cruise, over 130 sampling stations were occupied, at one of which were dredged manganese deposits with strong hydrothermal affinities. This is the first report of such deposits from an island arc setting.

Chemical composition of phosphorites, Fe-Mn nodules and crusts, and basalts from the West Pacific

The monograph gives the first systematic description of ore-bearing guyots from the West Pacific. It is mostly based on data obtained in numerous expeditions of Russian vessels during 1984-1992. Ore deposits located on upper parts of all slopes and tops of the guyots include phosphorites associated with cobalt- and platinum-rich ferromanganese crusts. Location, origin and prospecting of mineral deposits are discussed on the base of new data on metallogenic factors (geodynamics, tectonics, magmatism, sedimentation and morphostructures).

Nd and Sr isotope compositions, REE concentrations and Al/Ca ratios of different phases of surface sediments in the South Pacific

The radiogenic isotope composition of neodymium (Nd) and strontium (Sr) are useful tools to investigate present and past oceanic circulation or input of terrigenous material. We present Nd and Sr isotope compositions extracted from different sedimentary phases, including early diagenetic Fe-Mn coatings, "unclean" foraminiferal shells, fossil fish teeth, and detritus of marine surface sediments (core-tops) covering the entire midlatitude South Pacific. Comparison of detrital Nd isotope compositions to deep water values from the same locations suggests that "boundary exchange" has little influence on the Nd isotope composition of western South Pacific seawater. Concentrations of Rare Earth Elements (REE) and Al/Ca ratios of "unclean" planktonic foraminifera suggest that this phase is a reliable recorder of seawater Nd isotope composition. The signatures obtained from fish teeth and "nondecarbonated" leachates of bulk sediment Fe-Mn oxyhydroxide coatings also agree with "unclean" foraminifera. Direct comparison of Nd isotope compositions extracted using these methods with seawater Nd isotope compositions is complicated by the low accumulation rates yielding radiocarbon ages of up to 24 kyr, thus mixing the signal of different ocean circulation modes. This suggests that different past seawater Nd isotope compositions have been integrated in authigenic sediments from regions with low sedimentation rates. Combined detrital Nd and Sr isotope signatures indicate a dominant role of the Westerly winds transporting lithogenic material from South New Zealand and Southeastern Australia to the open South Pacific. The proportion of this material decreases toward the east, where supply from the Andes increases and contributions from Antarctica cannot be ruled out.

Cd/Ca ratios and element analyses of ODP Hole 115-709C

During three to four d18O cycles (determined on Globigerinoides ruber), more positive d18O (= higher global ice volume) values correlated with higher Globorotalia menardii percentages, total numbers of benthic foraminifers, number of benthic foraminifer species, and the percent of total foraminifers composed of benthic foraminifers. During the same intervals, barite and insoluble residues also generally recorded higher values; however, there was no clear evidence of systematic variation in cadmium/calcium ratios (in benthic foraminifers). Maximum percentages of Globigerinoides sacculifer and Globigerinoides ruber correlate with more negative d18O (= lower global ice volume) values, although they sometimes appear to lead the d18O changes by < =4,000 yr. The increase in percentage of the tropical "divergence" planktonic foraminifer species G. menardii and the reduction of the "nondivergence" tropical species G. ruber and G. sacculifer at times of inferred ice growth is attributed to periodic intensification of divergence associated with the Equatorial Counter Current. Barite and insoluble residue sedi- mentation at the site also generally show a relative increase at those times.

Element ratio (Sr/Ca, Ba/Ca, B/Ca, and Mg/Ca) profiles throughout the larval life stage of Mytilus edulis, 2011

Rising anthropogenic CO2 in the surface ocean has raised serious concerns for the ability of calcifying organisms to secrete their shells and skeletons. Previous mollusc carbonate perturbation experiments report deleterious effects at lowered pH (7.8-7.4 pH units), including reduced shell length and thickness and deformed shell morphology. It is not clear whether the reduced shell growth results from a decrease in calcification rate due to lowered aragonite saturation or from an indirect effect on mollusc metabolism. We take a novel approach to discerning between these two processes by examining the impact of lowered pH on the 'vital-effect' associated with element ratios. Reported herein are the first element ratio (Sr/Ca, Ba/Ca, B/Ca, Mg/Ca and Mn/Ca) profiles throughout the larval life stage of Mytilus edulis. Element ratio data for individuals reared in ambient conditions provide new insights into biomineralization during larval development. Sr/Ca ratios are consistent with Sr incorporation in the mineral phase. Mg and Mn are likely hosted in an organic phase. The Ba partition coefficient of early larval shells is one of the highest reported in biogenic aragonite. The reason for the high Ba concentrations is unknown, but may reflect the assimilation of Ba from food and/or Ba concentration in an organic or amorphous carbonate phase. There is no observable difference in the way the studied elements are incorporated into the shells of individuals reared in ambient and lowered pH conditions. The reduced growth rate at lower pH may be a consequence of a disruption to the larval mollusc metabolism.

Uranium and radioactive isotopes in bottom sediments and Fe-Mn nodules and crusts of seas and oceans

The main stages of the sedimentary cycle of uranium in modern marine basins are under consideration in the book. Annually about 18 thousand tons of dissolved and suspended uranium enters the ocean with river runoff. Depending on a type of a marine basin uranium accumulated either in sediments of deep-sea basins, or in sediments of continental shelves and slopes. In the surface layer of marine sediments hydrogenic uranium is predominantly bound with organic matter, and in ocean sediments also with iron, manganese and phosphorus. In diagenetic processes there occurs partial redistribution of uranium in sediments, as well as its concentration in iron-manganese, phosphate and carbonate nodules and biogenic phosphate detritus. Concentration of uranium in marine sediments of various types depending on their composition, as well as on forms of its entering, degree of differentiation and of sedimentation rates, on hydrochemical regime and water circulation, and on intensity of diagenetic processes.

Chemical composition of Fe-Mn ores from the North Pacific seamounts

Ore crusts from the Mid-Pacific Seamounts were studied by scanning electron microscopy and by atomic-absorption and chemical analysis. Characteristic ultramicroscopic structures of ore material of these crusts are globular, fibrous, conchoidal and cellular. Non-ore components are represented by fragments of bedrocks, zeolites, biogenic carbonates, and apatite. Contents of ore elements are: Fe 5.53-15.82%; Mn 14.92-23.45%; Co 0.32-0.82%; Ni 0.22-0.70%; Cu 0.02-0.12%, Mn/Fe ratio varies from 1.02 to 3.39. In general elevated contents of Co (>0.55%) in Fe-Mn crusts correspond to elevated (>1) Mn/Fe ratios.

Annotated record and spectrochemical analyses of Mn nodules from Georgia Strait, British Columbia obtained during CNAV Laymore in 1970

A study of the distribution, dispersal and composition of surficial sediments in the Strait of Georgia, B.C., has resulted in the understanding of basic sedimentologic conditions within this area. The Strait of Georgia is: a long, narrow, semi-enclosed basin with a restricted circulation and a single, main, sediment source. The Fraser. River supplies practically all the sediment now being deposited in the Strait of Georgia, the bulk of it during the spring and summer freshet. This river is building a delta into the Strait from the east side near the south end. Ridges of Pleistocene deposits within the Strait and Pleistocene material around the margins, like bedrock exposures, provide local sources of sediment of only minor importance. Rivers and streams other than the Fraser contribute insignificant quantities of sediment to the Strait. Sandy sediments are concentrated in the vicinity of the delta, and in the area to the south and southeast. Mean grain size decreases from the delta toward the northwest along the axis of the Strait, and basinwards from the margins. Silts and clays are deposited in deep water west and north of the delta front, and in deep basins northwest of the delta. Poorly sorted sediments containing a gravel component are located near tidal passes, on the Vancouver Island shelf area, on ridge tops within the Strait, and with sandy sediments at the southeastern end of the study area. The Pleistocene ridges are areas of non-deposition, having at most a thin veneer of modern mud on their crests and upper flanks. The southeastern end of the study area contains a thick wedge of shandy sediment which appears to be part of an earlier delta of the Fraser River. Evidence suggests that it is now a site of active submarine erosion. Sediments throughout the Strait are compositionally extremely similar, with-Pleistocene deposits of the Fraser River drainage basin providing the principal, heterogeneous source. Gravels and coarse sands are composed primarily of lithic fragments, dominantly of dioritic to granodloritlc composition. Sand fractions exhibit increasing simplicity of mineralogy with decreasing grain-size. Quartz, felspar, amphibole and fine-grained lithic fragments are the dominant constituents of the finer sand grades. Coarse and medium silt fractions have compositions similar to the fine sands. Fine silts show an increase in abundance of phyllosilicate material, a feature even more evident in the clay-size fractions on Montmorillonite, illite, chlorite, quartz and feldspar are the main minerals in the coarse clay fraction, with minor mixed-layer clays and kaolinite. The fine clay fraction is dominated by montmorillonite, with lesser amounts of illite and chlorite. The sediments have high base-exchange capacities, related to a considerable content of montmorillonite. Magnesium is present in exchange positions in greater quantity in Georgia Strait sediments than in sediments from the Fraser River, indicating a preferential uptake of this element in the marine environment. Manganese nodules collected from two localities in the Strait imply slow sediment accumulation rates at these sites. Sedimentation rates on and close to the delta, and in the deep basins to the northwest, are high.