Geochemistry of Rare Earth Elements in the Ocean

This work briefly outlines modern ideas on geochemistry of rare earth elements (REE) in the ocean. Sources of REE and chemical properties of these elements, which govern their migration ability in natural processes, are considered. The REE behavior in the river water–seawater mixing zone is analyzed. The fractionation of dissolved and suspended REE in oceanic water in both aerobic and anaerobic conditions is also considered. It is shown that the variability of REE composition in pelagic sediments reflects the fractionation of these elements in the oceanic water as a consequence of material differentiation in the ocean. The REE distribution in terrigenous, authigenic, hydrothermal, and biogenic constituents of sediments, such as clay, bone debris, barite, phillipsite, Fe–Mn oxyhydroxides (ferromanganese nodules and micronodules), Fe–Ca hydroxo-phosphate, diatoms, and foraminifers, is considered.     

Rare earth elements in the sedimentary cycle: A summary

The relative and absolute concentrations of rare earth elements (REE) in authigenic and biogenic phases of deep-sea sediments are quite different. Competition between these phases for REE has resulted in fractionation from the parent material, the latter consisting predominantly of terrigenous material, but with a contribution from marine volcanism. The strongest feature of this fractionation is a depletion of Ce, relative to La, in CaCO₃, opalline silica, phillipsite, phosphorite, barite, and montmorillonitic clays; and a Ce enrichment in Fe/Mn nodules. The distribution of REE in different masses of seawater strongly reflects their fractionation in sediments. Whereas the relative concentration of REE in rivers resembles that of shale, their removal from seawater by authigenic and biogenic phases results in: (1) a decrease of their total concentration; (2) a depletion of Ce; and (3) an enrichment of heavy REE relative to light REE. The order of fractionation for water masses in the Atlantic Ocean is:Antarctic intermediate water > North Atlantic deep water > Antarctic bottom water> shelf water > river water ～ shale.The shale-normalized pattern for the sum of REE in the authigenic and biogenic phases of pelagic sediment and in seawater resembles that of an admixture of shale and basalt corresponding presumably to the realtive inputs from continents and marine volcanism respectively. The estimated rate of accumulation of each REE in the sediment, however, is approximately 12 times the estimated rate of input of REE from these two sources.     

Geochemistry of the Manganese Ore Process in the Ocean: Evidence from Rare Earth Elements

Processes governing the formation of rare earth elements (REE) composition are considered for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different 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, the size of micronodules has a positive correlation with the Mn content and Mn/Fe and P/Fe ratios and a negative correlation with Fe, P, REE, and Ce anomaly. The behavior of REE in micronodules from sediments within bioproductive zones is related to increase of the influence of diagenetic processes in sediments as a response to the growth of the size of micronodules. Distinctions in the chemical composition of micronodules and nodules are related to their interrelations with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in the labile fraction of sediments reworked during diagenesis. Sources of the 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 the 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 the sorption of phosphate-ion from bottom and pore waters. The sorption of phosphate-ion results in an additional sorption of REE.     

Geochemistry of rare earth elements in micro-and macronodules from the pacific bioproductive zone

Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50–250, 250–500, and >500 μm), coexisting macronodules, and host sediments are examined. The samples were collected from three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of the surficial water. The influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, the Ce concentration inversely correlates with the micronodule fraction dimension and drops to the lowest value in macronodules and host sediments. The Ce decrease is generally accompanied by the Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with the micronodule dimension. The contribution of diagenetic source is maximal for macronodules. The REE signature distinctions of micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. The relationship and general trend in the chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.     

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean

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

Crystal chemistry of diagenetic zeolites in volcanoclastic deposits of Italy

Zeolites from the most important volcanoclastic deposits of Italy include: (1) phillipsite and heulandite from the cinerite of the central northern Apennines; (2) chabazite and phillipsite from the phonolitic tephritic ignimbrite with black pumices; (3) phillipsite from the “tufo lionato” of Vulcano Laziale; (4) chabazite and phillipsite from the Campanian ignimbrite; (5) phillipsite from the Neapolitan yellow tuff; and (6) chabazite and phillipsite from the pyroclastics of Monte Vulture. Compared with sedimentary phillipsites and chabazites described in the literature, the chabazites and phillipsites studied here have lower Si/Al ratios and higher K contents. These chemical peculiarities are correlated with both the K-rich vesuvitic-leucititic, latitic-phonolitic, and potassic alkali-trachytic chemistry of the ash from which they were derived and, very likely, with the character of the hydrologically open system environment in which they formed. The zeolite of the heulandite-clinoptilolite group from the cinerite of the central northern Apennines is classified as a true heulandite on the basis of its chemical composition and thermal behavior.     

Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.     

Rare earth element studies of surficial sediments from the southwestern Carlsberg Ridge,Indian Ocean

The rare earth element (REE) contents of sixteen surficial calcareous sediments from the southwestern Carlsberg Ridge, Indian Ocean, have been determined. The total REE vary from 35 ppm to 126 ppm and are inversely related to the calcium carbonate content. REEs show a strong positive correlation with Al + Fe + K + Mg + Na (r ²= 0.98) and Mn + Fe + Cu + Ni (r ²= 0.86) suggesting that the REE is associated with a combined phase of clays (mainly illite) and Mn-Fe oxyhydroxides. The aeolian input into these sediments is suggested from the weak positive Eu/Eu* anomaly. Shale-normalized (NASC) pattern along with La_(n)/Yb_(n) ratio suggest enrichment of heavy REE (HREE) relative to the light REE (LREE) with a negative Ce/Ce* anomaly implying retention of a bottom water REE pattern. An erratum to this article is available at .     

Rare Earth Element Enrichment in Late Archean Manganese Deposits from the Iron Ore Group,East India

The major, trace and rare earth element (REE) composition of Late Archean manganese, ferromanganese and iron ores from the Iron Ore Group (IOG) in Orissa, east India, was examined. Manganese deposits, occurring above the iron formations of the IOG, display massive, rhythmically laminated or botryoidal textures. The ores are composed primarily of iron and manganese, and are low in other major and trace elements such as SiO₂, Al₂O₃, P₂O₅ and Zr. The total REE concentration is as high as 975 ppm in manganese ores, whereas concentrations as high as 345 ppm and 211 ppm are found in ferromanganese and iron ores, respectively. Heavy REE (HREE) enrichments, negative Ce anomalies and positive Eu anomalies were observed in post‐Archean average shale (PAAS)‐normalized REE patterns of the IOG manganese and ferromanganese ores. The stratiform or stratabound shapes of ore bodies within the shale horizon, and REE geochemistry, suggest that the manganese and ferromanganese ores of the IOG were formed by iron and/or manganese precipitation from a submarine, hydrothermal solution under oxic conditions that occurred as a result of mixing with oxic seawater. While HREE concentrations in the Late Archean manganese and ferromanganese ores in the IOG are slightly less than those of the Phanerozoic ferromanganese ores in Japan, HREE resources in the IOG manganese deposits appear to be two orders of magnitude higher because of the large size of the deposits. Although a reliable, economic concentration technique for HREE from manganese and ferromanganese ores has not yet been developed, those ores could be an important future source of HREE.     

Phillipsite formation in nephelinitic rocks in response to hydrothermal alteration at Mount Etinde,Cameroon

Fresh nephelinitic rocks and hydrothermally altered rocks at Mount Etinde (Cameroon Volcanic Line, West Africa) have been studied by combined whole rock geochemistry (ICP-MS), mineralogy and mineral chemistry (SEM-EDS, WDS, XRD) techniques. The nephelinites have feldspathoids, clinopyroxene, perovskite and titanomagnetite as the principal minerals in the mode with subsidiary apatite and sphene. The mineralogy of their hydrothermally altered counterparts includes phillipsite, calcite and analcime which are secondary phases developed in response to hydrothermal fluid events. Correspondingly, the bulk rock geochemical data show elevated SiO₂, CaO, Na₂O and K₂O concentrations with increasing alteration and Al₂O₃ and Fe₂O₃ depletion while MgO, MnO and TiO₂ concentrations are largely unaffected. The nephelinites also have high concentrations of LILLE, HFSE and REE and upon hydrothermal alteration they show an enrichment of LREE and MREE over HREE. Phillipsite is the principal alteration mineral in the rocks and it occurs along cracks, vesicles and also forms alteromorphs after feldspathoids. The Ce content of these categories of phillipsite varies. Phillipsite along cracks is richer in Ce while phillipsite associated with calcite has lower Ce concentration and the phillipsite alteromorphs very little or no Ce. Various stages of fluid circulation are proposed hereby to explain the variations in phillipsite generation and composition.     

Geochemistry of mineralization with exchangeable REY in the weathering crusts of granitic rocks in South China

Mineralization with exchangeable rare earth element (REE) and yttrium (MEX-REY) has been recognized in the weathering profiles in South China since the early 1970's. This type of REY mineralization occurs in weathering profiles of parent rocks ranging in composition from granite to acidic volcanic rocks and lamprophyre. The majority of the known resources occurring in the weathering profiles of granitic rocks. Total resources of this type of REY amount to millions tons of rare earth oxides, and therefore represent one of the most important types of rare earth resources in China, particularly for heavy rare earth elements (HREE) and yttrium.Accumulation of REY in the weathering profiles of granitic rocks is strongly controlled by the resistance to weathering of the principal REY-bearing accessory minerals in the parent rocks; only a limited proportion of total REY (< 30%) is incorporated in the rock-forming minerals. MEX-REY more commonly occur in weathering profiles developed on granitic rocks within which most of the REY are incorporated in accessory minerals weakly resistant to weathering (doverite, parisite, etc.). For the well-developed weathering profiles, three horizons can be distinguished from surface downwards: the lateritic horizon (A), the weathered horizon (B), and the weathering front (C). Continuous leaching, coupled with low rate of denudation, results in the accumulation of REY in the subsurface horizons (the B and C horizons), and thus results in REE differentiation within the well-developed, layered, and mature weathering profiles. Exchangeable REY, which can be replaced by cations like NH⁴⁺ and Na⁺ etc. in electrolyte solutions and can be removed by complexing agents such as EDTA, are commonly the major form of REE occurrence in the B horizon. Cerium is enriched in the top layer (A horizon) and depleted in the subsurface horizons of the weathering profiles, most likely due to the oxidation of Ce(III) to Ce(IV) followed by cerianite formation or absorption onto clays and/or Fe and Al oxyhydroxides.     

Geochemistry of Rare Earth Elements in Ferromanganese Micro- and Macronodules from the Pacific Nonproductive Zone

Ferromanganese micro- and macronodules in eupelagic clays at Site 35 of the South Basin were examined in order to check the REE distribution during the ferromanganese ore formation in nonproductive zones of the Pacific Ocean. We studied host sediments and their labile fraction, ferromanganese micronodules (fractions 50–100, 100–250, 250–500, and >500 m) from eupelagic clays (horizons 37–40, 105–110, 165–175, and 189–190 cm), and buried ferromanganese micronodules (horizons 64–68, 158–159, and 165–166 cm). Based on phase analysis data, the anomalous REE enrichment of eupelagic clays from Site 35 is related to the accumulation of rare earth elements in iron hydroxophosphates. The Ce concentration, generally linked to manganese oxyhydroxides, is governed by the oxidation of Mn and Ce in oceanic surficial waters. Micronodules (Mn/Fe = 0.7–1.6) inherit compositional features of the labile fraction of sediments. The Ce, Co, and Th concentrations depend on the micronodule dimension. The enrichment of micronodules in hydrogenic or hydrothermal substance is governed by their dimension and the dominant source of suspended oxyhydroxide material. The study of buried ferromanganese micronodules revealed general regularities in the compositional evolution of oxyhydroxide matrices of ferromanganese micro- and macronodules. The compositional variation of micro- and macronodules, relative to the labile fraction of sediments, in the Pacific nonproductive zone dramatically differs from the pattern in bioproductive zones, where micronodule compositions in larger fractions are similar to those in associated macronodules and labile fractions of the host sediment as a result of the more intense suboxidative diagenesis.     

Partition coefficients for REE between garnets and liquids: implications of non-Henry's Law behaviour for models of basalt origin and evolution

Partition coefficients for the rare earth elements (REE) Ce, Sm and Tm between coexisting garnets and hydrous liquids have been determined at high pressure and temperatures (30 kbar and 1300 and 1500°C). Two synthetic systems were studied, Mg₃Al₂Si₃O₁₂-H₂O and Ca₃Al₂Si₃O₁₂-H₂O, in addition to a natural pyrope-bearing system.Deviations from Henry's Law behaviour occur at geologically relevant REE concentrations. At concentrations < 3 ppm Ce, < 12 ppm Sm, < 80 ppm Tm in pyrope and < 100 ppm Ce, < 250 ppm Sm, < 1000 ppm Tm in grossular (at 30 kbar and 1300°C), D^{garnet liquid}_REE increases as the REE concentration in the garnet decreases. At higher concentrations, D_REE is constant. D^{grossular liquid}_REE also constant when the garnet contains less than about 2 ppm Sm or Tm. The REE concentration at which D_REE becomes constant increases with increasing temperature, decreasing REE ionic radius and increasing Ca content of the garnet.Partitioning behaviour of Ce, Sm and Tm between a natural pyrope-rich garnet and hydrous liquid is analogous to that in the synthetic systems and substantiates the substitution model proposed by Harrison and Wood (1980).Values of D_REE^{garnet/liquid} for which Henry's Law is obeyed are systematically higher for grossular than for pyrope (D^{pyrope/liquid} = 0.067(Ce), 0.108(Sm), 0.155(Tm) and D^{grossular/Liquid} = 0.65(Ce), 0.75(Sm), 4.55(Tm).The implications of non-Henry's Law partitioning of REE for models of basalt petrogenesis involving garnet are far-ranging. Deviations from Henry's Law permit refinements to be made to calculated REE abundances once basic model parameters have been defined.     

Economically viable rare earth element deposits along beach placers of Andhra Pradesh,eastern coast of India

A comprehensive study was carried out in order to determine the radioelement and rare earth element (REE) concentrations in beach placer deposits at selected locations along the eastern coast of Andhra Pradesh in India. This was done to evaluate the economic value of these deposits. The findings of this study suggest that high Th and low K concentrations delineate the prospective regions having REE deposits. The beach placers, in general, can be characterized by high thorium and moderate uranium concentrations. The concentrations of REEs vary in the following order: Ce > La> Nd > Pr > Sm > Gd > Dy. Rapid in situ thorium prospectivity coupled with laboratory-based techniques like ICP-MS, as proposed in this study, would help in the identification of prospective REE sources along the coastal placers. The development of indigenous resources of light rare earth elements (LREEs), medium rare earth elements (MREEs), and heavy rare earth elements (HREEs) would decrease the dependence on imports, which have a strategic hold on the production and supply of the REEs, globally.     

Geochemistry of Rare Earth Elements and Thorium in Sediments and Ferromanganese Nodules of the Atlantic Ocean

The behavior of rare earth elements (REE) and Th is studied along the west–east transect at 22°N across the Atlantic Ocean. It is shown that both REE and Th contents, relative to Al (the most lithogenic element), increase toward the pelagic region. The increasing trend becomes more complicated due to variations in the content of biogenic carbonate that serves as a diluting component in sediments. The REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing a weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al + Mn + Fe) and (Fe + Mn)/Ti, do not reach critical values. Variations in the REE content and composition allowed us to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenetic type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th concentrations depend on Fe content in Atlantic sediments. Therefore, one can suggest that only a minor amount of phosphorus is bound in bone debris. The low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic, as compared with those in pelagic regions of the Pacific.     

Geochemical Characteristics of Apatite in Heavy REE‐rich Deep‐Sea Mud from Minami‐Torishima Area,Southeastern Japan

We have conducted geochemical and mineralogical investigations of the rare earth and yttrium (REY)‐rich mud from the Minami‐Torishima area in the Pacific in order to clarify the concentration of REY and their host‐phase in the mud. X‐ray diffraction analysis shows that the mud is mainly composed of phillipsite, fluorapatite, quartz, albite, illite and montmorillonite. Whole‐rock CaO, P₂O₅ and total REY contents of the mud are positively correlated. Relative abundance of apatite is also positively correlated to P₂O₅ and total REY contents. These correlations suggest that apatite is the main host of the P₂O₅ and REY in the mud. We make in situ compositional analyses of constituent minerals in the REY mud. The results show that the apatite is abundant in REY (9300–32,000 ppm) and is characterized by a negative Ce anomaly and enrichment in heavy rare‐earth elements. This abundance and composition of REY of the mud is similar those of fish debris apatites. In contrast, phillipsite is less abundant in REY (60–170 ppm). Therefore we conclude that the main REY host phase of the mud is apatite.     

甘肃北山南金山金矿床矿床成因研究

南金山金矿床产于北山岛弧构造带内海相火山碎屑岩之中。矿床的岩矿石微量元素组合为Ba、La、Ce、Sr、Nd、Sm、Zr、Hf、Y等不相容元素,各类岩石样品的分布曲线非常相似,都具有明显的Pb正异常,表明有较多的地壳物质的加入,并有明显的La,Ce,Ti负异常。稀土总量∑REE(不包括叶蜡石)变化范围为(9.91~221.86)×10-6,其配分形式均为明显右倾曲线,轻、重稀土分馏,轻稀土相对富集而重稀土相对亏损。稀土总量较高,说明矿区内稀土元素在随岩浆迁移的过程中,上升到地壳时有一定的损失。矿物流体包裹体的均一温度、盐度、压力、气相成分等特征研究表明,南金山金矿床成矿流体以中低温,中低盐度,且有大量大气降水加入为特征,为典型的浅成中低温热液矿床。     

Particle geochemistry in the Rainbow hydrothermal plume, Mid-Atlantic Ridge

We report the analysis of 18 large volume (500-1500 L) in situ filtered samples of particulate material from the largest hydrothermal plume on the Mid-Atlantic Ridge, overlying the ultramafic-hosted Rainbow hydrothermal field at 36° 14′N. Measured particulate iron concentrations reach 614 nM. High concentrations of particulate Fe oxyhydroxides result from the extremely high Fe concentration (∼24 mM) and Fe/H₂S ratio (∼24) of the vent fluids, and persist to at least 10 km away from the vent site due to the advection of plume material with the ambient along-axis flow. Two of the nine pairs of pump deployments appear to have intercepted the buoyant or otherwise very young portion of the hydrothermal plume. These samples are characterized by anomalously (compared to neutrally buoyant plume samples) high concentrations of Mg, U, and chalcophile elements, and low concentrations of Mn, Ca, V, Y, and the rare earth elements (REE). Within the neutrally buoyant plume, elemental distributions are largely consistent with previously observed behaviors: preferential removal of chalcophile elements, conservative behavior of oxyanions (P, V, and U), and continuous scavenging of Y and the REE. This consistency is particularly significant in light of the underlying differences in fluid chemistry between Rainbow and other studied sites. Chalcophile elements are preferentially removed from the plume in the order Cd>Zn>Co>Cu. Phosphorus/iron and vanadium/iron ratios for the neutrally buoyant plume are consistent with global trends with respect to the concentration of dissolved phosphate in ambient seawater. Comparison of buoyant and neutrally buoyant plume ratios with data from hydrothermal sediments underlying the Rainbow plume (Cave et al., 2002) indicates, however, that while P/Fe ratios are indeed constant V/Fe ratios increase progressively from early stage plume particles to sediments. REE distributions in the buoyant and neutrally buoyant plume appear most consistent with a continuous scavenging process during dispersion through the water column.     

Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements(REE) composition of the polymetallic crusts and nodules obtained from the South China Sea(SCS) were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances(∑REE) of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE(LREE), the markedly positive Ce anomaly(δCe), and the non-or weakly positive Eu anomaly(δEu), suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event(sea-level change) during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.     

High-resolution coral records of rare earth elements in coastal seawater: biogeochemical cycling and a new environmental proxy

In this study we have used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to produce a high resolution coral record of rare earth elements (REE), Mn and Ba from coastal Porites corals from the Great Barrier Reef of Australia. Validation of the LA-ICP-MS technique indicated that the method provides accurate and reproducible (RSD = 13-18%) analysis of low concentration REE in corals (∼1 to 100 ppb). The REE composition in coral samples was found to closely reflect that of the surrounding seawater and distribution coefficients of ∼1-2 indicated minimal fractionation of the series during incorporation into coral carbonate. To explore the idea that coral records of REE can be used to investigate dissolved seawater composition, we analyzed two coastal corals representing a total of ∼30 yr of growth, including a 10-yr overlapping period. Comparable results were obtained from the two samples, particularly in terms of elemental ratios (Nd/Yb) and the Ce anomaly. Based on this evidence and results from the determination of distribution coefficients, we suggest that useful records of seawater REE composition can be obtained from coral carbonates. When compared to the REE composition of a mid shelf coral, coastal corals showed a significant terrestrial influence, characterized by higher REE concentrations (greater than 10 times) and light REE enrichment. The REE composition of coastal seawater inferred from the coral record was dependent on seasonal factors and the influence of flood waters. REE fractionation displayed a strong seasonal cycle that correlated closely with Mn concentration. We suggest that higher Nd/Yb ratios and higher Mn concentrations in summer result from scavenging of heavy REE by particulate organic ligands and Mn reductive dissolution respectively, both processes displaying higher rates during periods of high primary productivity. The Ce anomaly also displayed a strong seasonal cycle showing an enhanced anomaly during summer and during flood events. This is consistent with the Ce anomaly being primarily controlled by the abundance of Ce oxidizing bacteria. Based on these arguments, we suggest that the coral record of dissolved REE and Mn may be regarded as a useful proxy for biological activity in coastal seawater.