Rare earth and other element contents and speciations in samples from Core AKO26-35, Pacific Ocean, Southwest Basin

Ferromanganese micro- and macronodules in eupelagic clays at Site AKO26-35 in the Southwest Pacific Basin were studied in order to check REE distribution during ferromanganese ore formation in non-productive zones of the Pacific Ocean. Host sediments and their labile fraction, ferromanganese micronodules (in size fractions 50-100, 100-250, 250-500, and >500 ?m) from eupelagic clays (horizons 37-10, 105-110, 165-175, and 189-190 cm), and buried ferromanganese micronodules (horizons 64-68, 158-159, and 165-166 cm) were under study. Based on partition analysis data anomalous REE enrichment in eupelagic clays from Site AKO26-35 is related to accumulation of rare earth elements in iron hydroxophosphates. Concentration of Ce generally bound with manganese oxyhydroxides is governed by oxidation of Mn and Ce in ocean surface waters. Micronodules (with Mn/Fe from 0.7 to 1.6) inherit compositional features of the labile fraction of bottom sediments. Concentrations of Ce, Co, and Th depend on micronodule sizes. Enrichment of micronodules in hydrogenic or hydrothermal matter is governed by their sizes and by a dominant source of suspended oxyhydroxide material. The study of buried ferromanganese micronodules revealed general regularities in compositional evolution of oxyhydroxide matrices of ferromanganese micro- and macronodules. Compositional variation of micro- and macronodules relative to the labile fraction of sediments in the Pacific non-productive zone dramatically differs from the pattern in bioproductive zones where micronodule compositions in coarser fractions are similar to those in associated macronodules and labile fractions of host sediments due to more intense suboxidative diagenesis.

(Table 1) Activity of alkali phosphatase in suspended matter at 20°C and environmental temperatures, and recycling time of organic phosphorus in the Barents and Norwegian seas

Alkali phosphatase activity and hydrochemical structure of waters in the Barents and Norwegian seas were investigated. In a sea with the seasonal bioproduction cycle alkali phosphatase activity is also seasonal, rising with trophic level of waters. At the end of hydrological and biological winter activity is practically zero. Alkali phosphatase activity is especially important in summer, when plankton has consumed winter supply of phosphate in the euphotic layer and nutrient limitation of primary production begins. In summer production and destruction cycle, apparent time for recycling of phosphorus by phosphatase in suspended matter in the euphotic layer of the Barents Sea and Norwegian Sea averages from 7 to 30 hours.

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.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

Geochemistry of minerals at DSDP Hole 70-504B

Hole 504B, drilled into the 5.9 Ma crust of the southern flank of the Costa Rica Rift, tapped a hydrothermal system in its conductive stage. Three alteration zones were encountered along the 561.5 meters of basement drilled. The upper alteration zone, 274.5 to 584.5 meters below the seafloor (BSF), is characterized by the presence of color zonation in which red halos are located between dark gray inner rock portions and dark gray outer bands. The red halos are characterized by an abundance of iddingsite, and they have higher K2O contents and Fe3+/FeT ratios, but lower SiO2 contents, than the adjacent dark gray inner zones. The dark gray outer bands are characterized by the presence of celadonite-nontronite. Saponite is omnipresent in these three alteration bands. Phillipsite is the only zeolite that occurs in the upper alteration zone. The upper alteration zone is interpreted as being the result of low-temperature alteration, with large amounts of cold oxygenated seawater percolating through the upper ocean crust. In the upper alteration zone, the formation of red halos was both preceded and followed by formation of dark gray outer bands. Then followed formation of dark gray cores. The lower alteration zone (584.5-835.5 m BSF) is characterized by the absence of color zonation, the downward-increasing abundance of pyrite and saponite, and the presence of quartz, talc, and calcite. The chemical changes (downhole MgO enrichment and concomitant CaO depletion) observed in the basalts of the lower alteration zone are thought to result from reactions of oceanic basalts with evolved seawater (i.e., solutions derived from seawater that has already reacted with ocean crust), which is thus depleted in oxygen, potassium, and radiogenic strontium. This alteration process, which was responsible for saponite formation in both the upper and lower alteration zones, was rock dominated, and it took place under suboxic to anoxic conditions during a second stage of alteration. Reaction temperatures could have progressively increased with depth. There is also a zeolitic zone that essentially coincides with the lower part of the upper alteration zone (between 528.5 and 563 m BSF). The host rock adjacent to veins of zeolite exhibits a greenish discoloration due to the intensive replacement of the igneous minerals. The replacement minerals result in significant increases in the bulk rock K2O, MgO, CaO, CO2, and H2O+ contents. The solutions circulating along the newly opened fissures had high Ca activity, and minerals probably precipitated in these fissures at 60°C or 110°C. These hydrothermal solutions circulated later than those responsible for the formation of the minerals that characterize the upper and lower alteration zones.

Chemical composition of Fe-Mn nodules and host bottom sediments along the submeridional profile across the Brazil Basin

Sedimentation and ore formation were studied in sediments from nine stations located along the 24°W profile in the Brazil Basin of the Atlantic Ocean. Bottom sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to bottom sediments from other basins of the Atlantic Ocean, the sediments in study are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to decrease of Ce anomaly and LREE/HREE ratio. In reduced sediments preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crusts and ferromanganese nodules. Judging from contents of iron, manganese, REE, and other trace elements, these formations are ascribed to sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. Extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).

(Table 3) Contents of phosphorus, iron, and manganese in various zones of Fe-Mn nodules from the Pacific radiolarian belt

Phosphorus content in the surface layer of bottom sediments varies from 0.07% to 0.73%. Clayey radiolarian and radiolarian clayey oozes contain 0.12% P, miopelagic clays 0.21% P, and sediments with high iron and manganese concentrations 0.46% P (average contents). Phosphorus content of iron-manganese nodules varies from 0.14% to 0.39%, average 0.19%. Correlation between phosphorus contents in nodules and surrounding sediments is indicated indirectly by P/Fe ratio. Phosphorus is non-uniformly distributed in some nodules and sometimes correlates with iron. Accumulation of phosphorus in iron-manganese nodules is governed by a degree of manganese predominance in ore components.