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.     

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.     

Rare Earth Elements in Manganese Nodules from the Central Pacific Ocean

Manganese nodules in areas CP and CC of the central Pacific are rich in REE. Comparatively speaking,the REE contents of nodules in area CP are hihger than those in area CC; and the REE contents of nodulesfrom seamounts are higher than those of nodules from sea-floor plains and hills. Within the nodules, the REEshow a zonal distribution. The REE distribution patterns of the nodules are similar to those of the sedimentsand have a mirror image relationship with those of the sea water. Trivalent REE were not obviously differenti-ated when they entered into the nodules from the sea water.A major factor causing the difference of REE abundances between nodules and sediments is the redoxconditions. The redox intensity of the ocean floor of the Pacific is controlled mainly by Antarctic Bottom Wat-er(AABW), The iron-bearing facies in the nodules is the main carrier of REE.     

Rare earth elements distribution in fluorites and carbonate sediments of the east-alpine mid-triassic sequences in the Nördliche Kalkalpen

Controversial genetical interpretations on the fluorite occurrences in the leadzinc deposits of the Nördliche Kalkalpen led to the present study. The distribution of the rare-earth elements (REE) in the fluorspar-carbonate assemblages and the fluorspar separates have been determined non-destructively by means of instrumental neutron activation analysis using high resolution γ-spectrometry. A geochemical model describing the distribution of the REE in the two mineral phases of CaCO₃ and CaF₂ formed syngenetically under marine conditions has been built up in order to elucidate the observed REE abundances in the carbonates and their fluorspar separates. The low and comparable concentrations of REE, the similarity in their relative distribution patterns in carbonate-fluorspar assemblages as compared to those in carbonate sediments observed by other authors and the sedimentary characterization via the Tb/Ca-Tb/La relation criterion revealed by the present study unequivocally suggest a synsedimentary nature of the fluorspar. In addition, the study showed that a diagenetic recrystallization results in a further fractionation of Tb and La with a preferential improverishment in La. Such a phenomenon opens a possible geochemical criterion for the identification of different generations of fluorspars.     

太平洋中部富REY深海粘土的地球化学特征及REY富集机制

深海沉积物中的稀土资源是一种新发现的、潜在的海底稀土资源.对太平洋中部重力活塞取样获得的90个深海粘土样品的矿物组分、常量和稀土化学分析结果进行了系统分析,并与中北太平洋以及西北太平洋南鸟岛附近海域深海沉积物稀土元素地球化学特征进行了对比.研究结果表明:太平洋中部深海粘土以富含沸石、富P及富REY为特征,其碎屑矿物中含有较多的鱼牙骨,其P₂O₅与CaO之间、P₂O₅、CaO与∑REY之间呈良好的正相关关系;其稀土分布模式表现为明显的Ce负异常、一定程度的重稀土元素富集和Y正异常.太平洋中部深海粘土REY富集的主要原因是深海粘土中含有过量的磷酸盐组分,推测过量的磷酸盐组分是由于深海粘土中鱼牙骨碎屑的加入引起的.在北太平洋海域,未受到热液活动影响的条件下,富REY的深海沉积物的稀土元素富集机制具有统一性和普遍性,可以归纳为深海沉积物中高REY磷酸盐的混入作用.      

Do Archean chemical sediments record ancient seawater rare earth element patterns?

Rare earth elements (REE) concentrations of Archean and Proterozoic chemical sediments are commonly used as proxies to study secular trends in the geochemistry of Precambrian seawater. In addition, similarities in the REE signatures of Archean chemical sediments and modern seawater have led researchers to argue that some Archean rocks originated as biochemical precipitates (i.e., microbial carbonates) in shallow marine (e.g., peritidal) environments. However, terrestrial waters, including river water and groundwater, also commonly exhibit REE fractionation patterns that resemble modern seawater. Here, we present the seawater-like REE data for groundwaters from central México as additional evidence that these patterns are not unique to the marine environment. The shale-normalized REE patterns of the groundwaters are compared to those of modern seawater (open ocean and nearshore), Holocene reefal microbial carbonates and corals, and Archean chemical sediments using statistical means (i.e., ANOVA and Wilcoxon analyses) in order to quantify the similarities and/or differences in the REE patterns. Shale-normalized (SN) Ce anomalies and measures of REE fractionation [i.e., (La/Yb)_SN, (Pr/Yb)_SN, (Nd/Yb)_SN, and (Gd/Yb)_SN] of the central México groundwater samples are statistically indistinguishable from those of modern seawater. Moreover, except for differences in the Ce anomalies, which are lacking in Archean chemical sediments, the REE patterns of the central México groundwaters are also statistically similar to REE patterns of Archean chemical sediments, especially those of the 3.45 Ga Strelley Pool Chert. Consequently, we suggest that without additional information, it may be premature to unequivocally conclude that Archean chemical sediments record REE signatures of an Archean ocean.     

Geochemistry and mineralogy of REY-rich mud in the eastern Indian Ocean

Deep-sea sediments in parts of the Pacific Ocean were recently found to contain remarkably high concentrations of rare-earth elements and yttrium (REY) of possible economic significance. Here we report similar REY-rich mud in a core section from Deep Sea Drilling Project Site 213 in the eastern Indian Ocean. The sediments consist mainly of siliceous ooze, with subordinate zeolitic clay that contains relatively high REY concentrations. The maximum and average total REY (ΣREY) contents of this material are 1113 and 629 ppm, respectively, which are comparable to those reported from the Pacific Ocean. The REY-rich mud at Site 213 shows enrichment in heavy rare-earth elements, negative Ce anomalies, and relatively low Fe₂O₃/ΣREY ratios, similar to those in the Pacific Ocean. In addition, the major-element composition of the Indian Ocean REY-rich mud indicates slight enrichment in lithogenic components, which probably reflects a contribution from southern African eolian dust. A volcaniclastic component from neighboring mid-ocean ridges or intraplate volcanoes is also apparent. Elemental compositions and X-ray diffraction patterns for bulk sediment, and microscopic observation and elemental mapping of a polished thin section, demonstrate the presence of phillipsite and biogenic apatite, such as fish debris, in the REY-rich mud. The strong correlation between total REY content and apatite abundance implies that apatite plays an important role as a host phase of REY in the present deep-sea sediment column. However, positive correlations between ΣREY and elements not present in apatite (e.g., Fe₂O₃, MnO, and TiO₂) imply that the REY-rich mud is not formed by a simple mixture of REY-enriched apatite and other components.     

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 elements in fine-grained sediments of major rivers from the high-standing island of Taiwan

Thirty-eight sediment samples from 15 primary rivers on Taiwan were retrieved to characterize the rare earth element (REE) signature of fluvial fine sediment sources. Compared to the three large rivers on the Chinese mainland, distinct differences were observed in the REE contents, upper continental crust normalized patterns and fractionation factors of the sediment samples. The average REE concentrations of the Taiwanese river sediments are higher than those of the Changjiang and Huanghe, but lower than the Zhujiang. Light rare earth elements (LREEs) are enriched relative to heavy rare earth elements (HREEs) with ratios from 7.48 to 13.03. We found that the variations in (La/Lu)_UCC–(Gd/Lu)_UCC and (La/Yb)_UCC–(Gd/Yb)_UCC are good proxies for tracing the source sediments of Taiwanese and Chinese rivers due to their distinguishable values. Our analyses indicate that the REE compositions of Taiwanese river sediments were primarily determined by the properties of the bedrock, and the intensity of chemical weathering in the drainage areas. The relatively high relief and heavy rainfall also have caused the REEs in the fluvial sediments from Taiwan to be transported to the estuaries down rivers from the mountains, and in turn delivered nearly coincidently to the adjacent seas by currents and waves. Our studies suggest that the REE patterns of the river sediments from Taiwan are distinguishable from those from the other sources of sediments transported into the adjacent seas, and therefore are useful proxies for tracing the provenances and dispersal patterns of sediments, as well as paleoenvironmental changes in the marginal seas.     

Geochemistry of ferromanganese nodule–sediment pairs from Central Indian Ocean Basin

Fourteen ferromanganese nodule–sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule–sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo – (307, 273), Ni – (71, 125), Mn – (64, 87), Cu – (43, 80), Co – (23, 75), Pb – (15, 24), Zn – (9, 11) and V – (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation (r ? 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.     

A method for quantitative evaluation of carbonate dissolution in deep-sea sediments and its application to paleoceanographic reconstruction

A method is proposed by which the degree of attrition of the tests of certain foraminifera species, such as Globorotalia menardii and Globorotalia tumida, is used to “scale” the amount of CaCO₃ that has been dissolved from sediment. The scale is calibrated experimentally in the laboratory. The method has been applied to three calcareous cores from the Pacific and the Indian Oceans. It is shown that the original CaCO₃ contents in these cores were high (82–95%) and relatively uniform compared to the present down-core values. About 65 to 85% of the originally deposited CaCO₃ has been dissolved, corresponding to dissolution rates on the order of 0.1-0.3 moles/cm²/yr. These results indicate that appreciable solution could have occurred on sea floor rich in calcareous sediments and that the variation in CaCO₃ content in a core may have resulted largely from dissolution. The difference in the degree of solution between glacial and interglacial sediments in these cores is not so distinct, with ? 10% less intense dissolution during glacial times on the average. However, the dissolution minimum occurring around the late Wisconsin glaciation (10,000–20,000 yr B.P.) previously noted in several cores elsewhere is confirmed. At that time, near the site of core M70 PC-20 in the southwest Pacific, the $\text{CO}{}_3{}^{\mathrm{2?}}$ concentration of the bottom water is estimated to have been approximately 5% higher than the present value, and the calcite lysocline was about 300 m deeper. To evaluate possible variations in CaCO₃ deposition rate across the glacial-interglacial transitions requires precise age control, which the present study lacks.     

Geochemistry of a piston core from Ontong Java Plateau (western equatorial Pacific): evidence for sediment redistribution and changes in paleoproductivity

We discuss geochemical proxies, reflecting processes of primary productivity, CaCO₃ dissolution, and sediment redistribution in a piston core (RNDB 74P) from the Ontong Java Plateau. Due to the shallow water depth, biogenic carbonate is well preserved and a very goodδ ¹⁸O stratigraphy is available down to isotopic stage 11.²³⁰Th_ex gives evidence that the sediment accumulation pattern is driven mainly by processes of sediment focusing or winnowing. Due to the constant production of²³⁰Th in the water column, the bulk sediment accumulation rates could be corrected for the particle rain deriving from the water column above. The²³⁰Th_ex ⁰/CaCO₃ ratio reflects the well-known Pacific CaCO₃ preservation pattern with ice growth dissolution spikes and deglacial preservation spikes. The record of the grain size fraction >63 μm supports these results. The downcore concentrations and accumulation rates of barium (Ba) are on a higher level during interglacials and show several peaks. Normalization of Ba with²³⁰Th_ex ⁰ delivers a more uniform level of the Ba accumulation rates throughout the core. This pattern suggests a constantly higher biological productivity (nearly tenfold) in this area throughout the past 200 kyr compared with an open ocean environment. Barium peaks observed at the climatic transitions 2/1 and 6/5 and in stage 5 are in contrast to a predicted reduction of interglacial productivity at this location. A possible explanation might be the onset of the modern circulation pattern. The transition from Ba-enriched deep water to lower contents in the Atlantic might have resulted in an enhanced deposition of Ba in the Pacific.     

Rare earth elements and strontium isotopes of polymetallic nodules from southeastern Pacific Ocean

Rare earth element (REE) distributions and ⁸⁷Sr/⁸⁶Sr ratios were determined for nodule crusts and associated surface sediments collected in the southeastern Pacific Ocean between South America and the Tuamotu archipelago. The shale-normalized patterns of the REE from the surface sediments show pronounced negative anomalies in Ce which indicate a marine origin. One ⁸⁷Sr/⁸⁶Sr ratio also has a value characteristic for seawater strontium. REE patterns from the nodule crusts, when normalized to shales, seawater or associated surface sediment, show that a marine origin can also be proposed for the oxy-hydroxides. Only the Ce shows a systematic scatter, which could be the result of fluctuations in the oxidation-reduction conditions during nodule growth. The marine origin for REE is corroborated by the ⁸⁷Sr/⁸⁶Sr ratios which average 0 · 70905 ± 0 · 00019 (2σ), a value close to the seawater ⁸⁷Sr/⁸⁶Sr ratio of 0·70910 ± 0 · 00035. If the major metals of the polymetallic nodules have the same origin as these trace elements, then a direct precipitation from seawater can be postulated for the crusts studied here.     

Ferromanganese oxide deposits from the Central Pacific Ocean,II. Nodules and associated sediments

Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO₂-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO₂ nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.     

Sources of stream sediments in the granulite terrain of the Walawe Ganga Basin,Sri Lanka,indicated by rare earth element geochemistry

Thirty-eight samples of stream sediments draining high-grade metamorphic rocks in the Walawe Ganga (river) Basin, Sri Lanka, were analysed for their REE contents, together with samples of metamorphic suites from the source region. The metamorphic rocks are enriched in light REE (LREE) compared to heavy REE (HREE) and are characterised by high La/Lu ratios and negative Eu anomalies. The chondrite-normalised patterns for these granulite-grade rocks are similar to that of the average post-Archaean upper crust, but they are slightly enriched with La and Ce. The REE contents of the <63-μm fraction of the stream sediments are similar to the probable source rocks, but the other grain size fractions show more enriched patterns. The <63-μm stream sediments fraction contains lower total REE, more pronouncd negative Eu anomalies, higher Eu_N/Sm_N and lower La _N/Lu_N ratios relative to other fractions. The lower La _N/Lu_N ratio is related to the depletion of heavy minerals in the <63-μm fraction. The 63–125-μm and 125–177-μm grain size fractions of sediments are particularly enriched in LREE (average ΣLREE=2990 μg/g and 3410 μg/g, respectively). The total HREE contents are surprisingly uniform in all size fractions. However, the REE contents in the Walawe Ganga sediments are not comparable with those of the granulite-grade rocks from the source region of the sediments. The enrichment of REE is accounted for by the presence of REE containing accessory mineral phases such as zircon, monazite, apatite and garnet. These minerals are derived from an unknown source, presumably from scattered bodies of granitic pegmatites.     

Geochemistry of rare earth elements in oceanic phillipsites

The behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southern Basin of the Pacific. The REE concentrations were determined in the >50-μm-fraction phillipsite samples by the ICP-MS method. The composition of separate phillipsite accretions was studied using the electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite-only samples are related to the admixture of ferrocalcium hydroxophosphates. The analysis of separate phillipsite accretions reveals low (<0.1–18.1 ppm) REE (III) concentrations. The Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE (III) are present as an admixture of iron oxyhydroxides in separate phillipsite accretions. Based on the REE (III) concentration in iron oxyhydroxides, we can identify two generations of phillipsite accretions. Massive rounded accretions (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) accretions are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of the volcaniclastic material and oceanic deep water. Hence, the REE distribution in phillipsites does not depend on the sedimentation rate and host sediment composition.     

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.     

Geochemical Characteristics and Sedimentary Environment of the Salawusu Section

The chemical compositions of and the contents of CaCO3, free Fe2O3 and REE in the sediments of the Salawusu section have been analyzed to investigate the geochemical features of different sedimentary facies and explore their sedimentary enironmetnts during the Late Pleistocene.The con-tents of CaCO3, free Fe2O3 and ∑REE in lacustrine deposits of the middle part of the section are higher than those in the other parts ,except SiO2 which shows an opposite trend.According to the distribution characteristics of the components mentioned above, the section may be divided into four parts which are equivalent to those divided in terms of lithologic characters and sedimentary facies.More remarkable characteristics were observed with respect to the distribution of CaCO3, free Fe2O3,∑REE and SiO2/Al2O3 and FeO/Fe2O3 ratios, which can be adopted as the geochemical indices for paleoclimate division.From the above, four paleoclimate stages have been distinguished for the deposition process.The first stage ,dated at 0.20-0.15Ma, is characterized by a dry and cold climate,the second stage, ranging from 0.15 to 0.07 Ma ,by a warm and slightly dry climate,the third stage ,about 0.07-0.01Ma ,by a cold and humid climate;and prevailing in the last ten thorsand years is the fourth stage,with the climate changing graduall from warm-humid to warm-dry.     

Rare earth element patterns in manganese nodules and micronodules from northwest Atlantic

The shale-normalized REE patterns of manganese nodules from the northwest Atlantic show enrichment in Sm and Eu relative to the heavier and lighter REE, excluding Ce, and are similar to the patterns previously observed in deep water (> 3000m) nodules from the Pacific. The inverse relation of this pattern to that of sea water and the high Ce anomaly (average 5.5) indicate that probably the REE in the nodules originate from sea water and the nodules are possibly hydrogenous. The patterns for micronodules are similar to those of the nodules but the concentrations of REE were substantially higher in two of them.The red clay occurring on abyssal hills where nodules and micronodules are found also shows higher REE concentrations over terrigenous gray clay. The latter is devoid of nodules and micronodules and occurs in abyssal plains. The excess REE in the red clay also show a pattern similar to those of the nodules and micronodules. Most of the micronodule samples show a lower Ce anomaly (1.7) and lower Co concentration compared to the nodules, so it is inferred that at least some micronodules were formed during post-depositional periods when the conditions were less oxidizing than average.