Description and geochemistry of DSDP Leg 55 Holes

One of the objectives of Leg 55 was to investigate the Tertiary history of sedimentation and environment on the Emperor Seamounts after their volcanic activity. For the three first sites, 430, 431, and 432, drilled on Ojin, Nintoku, and Yömei Seamounts, the Neogene sedimentary deposits are not well represented and are not typical pelagic sediments. Except for two holes (430A and 432), where we found calcareous oozes, the sediments are heterogeneous sands, gravels, and pebbly mudstones with a wide range in grain size and composition. Two phenomena characterize these deposits: the inheritance of volcaniclastic material and its alteration, and the authigenesis of secondary minerals including silicates, phosphates, and ferromanganese oxides formed under volcanic influence in a marine environment.

Description of the fossil manganese nodules found in the Oligocene clay deposits of Moravia, Brno area, Czech Republic

In the green Oligocene clay of Krizanovice (former Krzyzanowicz) the author found numerous black nodules. In the 3-4 centimeter thick black crust of a particular specimen the concentration in MnO2 is evaluated at 46.6% MnO2. The determination was done using the Volhard's method (precipitation of Fe by ZnO and titration with KMnO4). Only the dissoleved part in HCL was analysed. The non soluble residue was essentially a silica precipitate in the form of many gray flakes. The specific gravity of the crust was evaluated at 3.8. In the internal yellow core the amount of manganese is about 2.39% MnO2. Due to the light color it is judged to probably be in the form of Mn2O3.

Observation of manganese deposits made during the 1936 transect of C/S Lord Kelvin through the Northern Atlantic Ocean

In May and June 1936 Dr. C. S. Piggot of the Geophysical Laboratory, Carnegie Institution of Washington, took a series of 11 deep-sea cores in the North Atlantic Ocean between the Newfoundland banks and the banks off the Irish coast. These cores were taken from the Western Union Telegraph Co.'s cable ship Lord Kelvin with the explosive type of sounding device which Dr. Piggot designed. All but two of these cores (Nos. 8 and 11) are more than 2.43 meters (8 feet) long, and all contain ample material for study. Of the two short cores, No. 8 was taken from the top of the Faraday Hills, as that part of the mid-Atlantic ridge is known, where the material is closely packed and more sandy and consequently more resistant; No. 11 came from a locality where the apparatus apparently landed on volcanic rock that may be part of a submarine lava flow.

Description and chemical composition of manganese nodules in a core located in the Nares Abyssal Plain, Atlantic Ocean

Three nodules from a core taken north of Puerto Rico are composed chiefly of an x-ray amorphous, hydrated, iron-manganese oxide, with secondary goethite, and minor detrital silicates incorporated during growth of the nodules. No primary manganese mineral is apparent. The nodules are enriched in iron and depleted in manganese relative to Atlantic Ocean averages. The formation of these nodules appears to have been contemporary with sedimentation and related to volcanic activity.

Description and 238U, 234U, 232Th and 230Th measurements of the manganese nodule analysed from station SO79_63KG, R/V SONNE

Thorium and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution Th-230(excess) profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06-0.59 ppb (Th-230), 0.43-1.40 ppm (Th-232), 0.09-0.49 ppb (U-234) and 1.66-8.24 ppm (U-238). The uranium activity ratio in the uppermost samples (1-6 mm) and in two further sections in the nodule at 12.5+/-1.0 mm and 27.3-33.5 mm comes close to the present ocean wa ter value of 1.144+/-0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the Th-230(excess) concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant Th-230(excess) concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11-15 and 28-33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable sb supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.

Illustration of manganese nodules and crust collected from the Suiko Seamount, Northwestern Pacific Ocean

An initial investigation has been undertaken on the chemical composition of the manganese nodules. The results of chemical analyses on each layer of single nodules reveal the periodic patterns of distribution for Mn, Fe, Cu, Pb, Zn, Ni and Co contents. The variations strongly suggest that those of the elements in nodules from this region are, at least, climatically controlled.

Illustration of manganese nodules and crust collected from the Suiko Seamount, Northwestern Pacific Ocean

Manganese nodules from the Suiko Seamount exhibit the significant characteristics in mineral compositions. Well crystallized todorokite and birnessite, which are principal manganese mineral phase in nodules, only occur in the oxide layer directly incasing pebbles and coarse sand. The preferential formation of todorokite or birnessite phases seem to be principally controlled by the reaction rate of iron-manganese oxides with trace elements such as Cu, Ni, Co, Zn, Pb concentrated in nodules, rather than redox characteristics of sedimentary environment or mineralogical diagenetic process.

(Table 1, page 437) Chemical composition of manganese encrusted Rhabdammina tubes in Eastern Mediterranean off Cyprus

Study of cores taken from the north-eastern Mediterranean during cruise 4/72 of the RRV Shackleton, using a Lehigh 4-inch hydroplastic gravity corer and containing layered organic structures encrusted with either manganese or iron minerals.

(Table 1, page 168) Iron, manganese, and phosphorus concentrations in Fe-Mn-concretions from the Gulf of Bothnia, northern Baltic Sea

Fe-Mn-concretions of a spheroidal type were found according to electron probe determinations to consist of alternating iron- and manganese-rich layers. This pattern was ascribed to seasonal variations in the physico-chemical conditions governing the precipitation of the hydrous oxides of iron and manganese. Calculations based on the rhythmic growth of the concretions investigated gave a mean accumulation rate of 0.15-0.20 mm/yr. The rather high phosphorus content (average 3.5 % P2O5) of the concretions was found to be concentrated in the iron-rich layers, probably as a result of the scavenging effect of ferric hydroxide.

(Figure 2) Dissolved manganese concentrations during POLARSTERN Cruise ANT-XXIV/3

The first comprehensive dataset (492 samples) of dissolved Mn in the Southern Ocean shows extremely low values of 0.04 up to 0.64 nM in the surface waters and a subsurface maximum with an average concentration of 0.31 nM (n=20; S.D.=0.08 nM). The low Mn in surface waters correlates well with the nutrients PO4 and NO3 and moderately well with Si(OH)4 and fluorescence. Furthermore, elevated concentrations of Mn in the surface layer coincide with elevated Fe and light transmission and decreased export (234Th/238U deficiency) and fluorescence. It appears that Mn is a factor of importance in partly explaining the HNLC conditions in the Southern Ocean, in conjunction with significant controls by the combination of Fe limitation and light limitation. No input of Mn from the continental margins was observed. This is ascribed to the protruding continental ice sheet that covers the shelf and shuts down the usual biological production, microbial breakdown and sedimentary geochemical cycling. The low concentrations of Mn in the deep ocean basins (0.07-0.23 nM) were quite uniform, but some elevations were observed. The highest deep concentrations of Mn were observed at the Bouvet Triple Junction region and coincided with high concentrations of Fe and are deemed to be from hydrothermal input. The deep basins on both sides of the ridge were affected by this input. In the deep Weddell Basin the input of Weddell Sea Bottom Water appears to be the source of the slightly elevated concentrations of Mn in this water layer.

(Fig 1, page 350) A manganese nodule in the top part of the CHUBASCO station 17 core taken in the Pacific Ocean

The vast extent of pelagic deposits, covering about 70 per cent of the ocean floor, thus about half of the earth, makes them of obvious importance to all Earth Science. All the pelagic (eupelagic) sediments, whether largely of plankton remains or fine inorganic particles, have certain distinctive characteristics to reflect their environment of accumulation. The great segregation of manganese in pelagic sediments presents many problems. It is hypothesized that in the formation of present day nodules a relatively slow accumulation in order to permit deposition of more of the manganese as large nodules, rather than as the disseminated micronodules that are in larger proportion in the Tertiary.

(Table 2) Oxygen isotope composition of authigenic and detrital phosphates from ODL Leg 201 sites

Many (bio)geochemical processes that bring about changes in sediment chemistry normally begin at the sediment-water interface, continue at depth within the sediment column and may persist throughout the lifetime of sediments. Because of the differential reactivity of sedimentary phosphate phases in response to diagenesis, dissolution/precipitation and biological cycling, the oxygen isotope ratios of phosphate (d18OP) can carry a distinct signature of these processes, as well as inform on the origin of specific P phases. Here, we present results of sequential sediment extraction (SEDEX) analyses combined with d18OP measurements, aimed at characterizing authigenic and detrital phosphate phases in continental margin sediments from three sites (Sites 1227, 1228 and 1229) along the Peru Margin collected during ODP Leg 201. Our results show that the amount of P in different reservoirs varies significantly in the upper 50 m of the sediment column, but with a consistent pattern, for example, detrital P is highest in siliciclastic-rich layers. The d18OP values of authigenic phosphate vary between 20.2 per mil and 24.8 per mil and can be classified into at least two major groups: authigenic phosphate precipitated at/near the sediment-water interface in equilibrium with paleo-water oxygen isotope ratios (d18Ow) and temperature, and phosphate derived from hydrolysis of organic matter (Porg) with subsequent incomplete to complete re-equlibration and precipitated deeper in the sediments column. The d18OP values of detrital phosphate, which vary from 7.7-15.4 per mil, suggest two possible terrigenous sources and their mixtures in different proportions: phosphate from igneous/metamorphic rocks and phosphate precipitated in source regions in equilibrium with d18Ow of meteoric water. More importantly, original isotopic compositions of at least one phase of authigenic phosphates and all detrital phosphates are not altered by diagenesis and other biogeochemical changes within the sediment column. These findings help to understand the origin and provenance of P phases and paleoenvironmental conditions at/near the sediment-water interface, and to infer post-depositional activities within the sediment column.