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 1. Concentration of rare earth elements in ferromanganese nodule (crust), sediment and rock of the South China Sea

Based on the X-ray fluorescence spectrum analysis of 15 rare earth elements in 6 ferromanganese nodu1es and 5 ferro mangane se crusts from the South China Sea, their abundances, distribution patterns, sources and relationships with associated elements are discussed in detail in this paper. The results show that: 1) The average abundance of rare earth elements in ferromanganese nodu1es and crusts is 1. 625 g/kg and 2. 167 g/kg respectively, which is 1-2 tim es , 5-6 times and 15-20 times higher than that in the Pacific, in the sediments of the North Pacific and the South China Sea, respectively; 2) The distribution patterns of rare earth elements standardized by the globular aerolite in ferro mangane se nodules and crusts are basically similar, that is, Ce is positively abnormal and Eu is in deficit slightly; 3) The relationships between rare earth elements and associated elements, sediments and rocks show that the source of rare earth elements in ferromanganese nodules and crusts have mainly come from slow deposition caused by weathering and leaching of medium acidic rock of the South China Sea.

Contents of rare earth and other chemical elements in Fe-Mn micronodules, nodules, and bottom sediments from the Clarion-Clipperton ore province in the Pacific Ocean

Processes governing the formation of rare earth element (REE) composition are under consideration for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different size fractions) within the Clarion-Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity size of micronodules has positive correlation with Mn content and Mn/Fe and P/Fe ratios and negative correlation with Fe, P, REE, and Ce anomaly. Behavior of REE in micronodules from sediments within bioproductive zones is related to increase of influence of diagenetic processes in sediments as a response to the growth of size of micronodules. Distinctions in chemical composition of micronodules and nodules are related to their interaction with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in labile fraction of sediments reworked during diagenesis. Sources of material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to sorption of phosphate-ion from bottom and pore waters. Sorption of phosphate-ion results in additional sorption of REE.

Rare earth and trace elements in igneous and metamorphic minerals of oceanic gabbros from the Mid-Atlantic Ridge

SIMS analyses have been carried out on clinopyroxenes, plagioclases and amphiboles of six gabbroic samples from Holes 921-924 of the Ocean Drilling Program Leg 153 sited in the MARK area of the Mid-Atlantic Ridge at the ridge-transform intersection, to investigate the rare earth, trace and volatile element distribution in the lower ocean crust during igneous crystallization and higher grade metamorphic conditions. The metagabbros underwent granulite to subgreenschist facies conditions through three main tectono-metamorphic phases: (1) ductile regime (750 < T < 1000 °C and P = 0.3 GPa); (2) transitional regime (600 < T < 700 °C and P = 0.2 GPa); (3) brittle regime (350 < T < 600 °C and P < 0.2 GPa). Igneous clinopyroxenes show Cl-chondrite normalized patterns depleted in LREE, and nearly flat for HREE. The rare earth and trace element distributions in igneous clinopyroxenes and plagioclases indicate that these minerals act as REE reservoirs, and comprise the main contribution to the overall rock content. The abundances in igneous minerals reflect the degree of fractionation of the parent liquids. In metamorphic clinopyroxenes recrystallized in anhydrous assemblages, the REE and trace elements patterns mimic those of the primary ones. Conversely, clinopyroxerie re-equilibrated in amphibolebearing assemblages shows a significant increase in REE, Ti, Zr, Y and V, a negative Eu anomaly, and slight decreases in Sr and Ba. An overall increase of REE and some trace elements is evident in hydrous assemblages, with preferential partitioning in the amphibole. It shows high Ti (18196-22844 ppm), LREE depleted patterns and LaN/SmN = 0.10-0.33, LaN/YbN = 0.10-0.30. Amphiboles from granoblastic assemblages show homogeneous patterns with no or a positive anomaly for TiN and negative anomalies for SrN and ZrN. Volatiles in amphibole are low, with Cl/F < 1; H2O% is significantly lower than the stoichiometric ratio (1.33-1.53%). The composition of the clinopyroxene and amphibole recrystallized in low-strain domains records evidence of incomplete re-equilibration, and element diffusion and partitioning is in part controlled by the textural site. The possible origins of the fluids involved in the metamorphic recrystallization are discussed: (1) remobilization from igneous amphibole; (2) exsolution from evolved melts; (3) introduction of seawater-derived fluids modified in rock-dominated systems; (4) injection of highly evolved hydrous melts during the metamorphic process.

Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Rare earth element data for sediments from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. Sum REE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlates slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and La_n/Yb_n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.