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.     

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 trace element in carbonaceous sediments from recent seas and oceans

Published and original data on the contents of 50 elements in carbonaceous sediments from seas (Black, Baltic, and Caspian) and fertile oceanic shelves (shelves of Namibia, Peru, Chile, and California) are generalized. The comparison of these results with the average composition of ancient carbonaceous shales reveals both similarities and differences in the distribution of indicator trace elements (Re, Hg, Se, Ag, Cd, Tl, U, Mo, As, Ni, and Zn). Correlation coefficients were analyzed to determine the characteristic element associations. It is established that oceanic carbonaceous sediments are closer in composition to carbonaceous shales than their marine analogues, which is related to the differences in sedimentation conditions, including hydrological, hydrochemical, and biogeochemical factors. The role of anoxic environment in the accumulation of chalcophile elements in sediments is estimated. The comparison of the contents of some mobile trace elements in oceanic water and carbonaceous sediments of modern oceans demonstrates that the water composition affects the composition of carbonaceous sediments and can be used for deciphering the composition of ancient ocean water.     

表生过程中水的稀土元素行为及其再分配

ＲＥＥ是了解和研究地球表生过程的一个重要手段。通过ＲＥＥ的化学性质、物源和在表生水中的迁移和分配，综述了ＲＥＥ在表生过程水中的独特行为和再分配的全过程，同时利用表生水作用的代表产物——页岩，讨论了ＲＥＥ在水与古沉积物中的作用和指示意义。由于ＲＥＥ测试方法中存在的问题，指出了过去研究中可能错误的结论和当前重新评估ＲＥＥ在水和岩石圈演化中分配及其地质意义的重要性     

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 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.     

稀土元素指标δCe－ΣREE对沉积相的指示研究

通过对内蒙古额济纳盆地小狐山剖面沉积物中酸溶组分稀土元素含量及其相关指标、分布模式的分析,讨论了剖面中稀土元素指标δCe－ΣREE与沉积相、沉积环境之间的关系。分析结果表明剖面沉积物酸溶组分中稀土元素丰度均值为7.24μg/g(不包括Y),其中LREE含量占稀土总量的88.67%; 且各层的稀土分布模式均为轻稀土适度富集缓右倾斜型、Eu呈负异常模式,但各相位地层的LREE富集程度与分配模式存在差异。由于小狐山剖面中沉积地层的自身岩性、沉积粒径、矿物结构组成以及气候环境变化等因素均可能会引起REE分异。因此,通过δCe－ΣREE图并结合三次回归曲线,可以很好地将不同沉积相得物质有效的区分开来。小狐山剖面除极少数的几个样品(水下沉积砂)之外,其余的均落在三次多项式回归曲线上部; 而风成砂层则几乎全部落在回归曲线之下; 此外,对于风沙－河流作用下的混合样品也有较好识别,河流过渡相的样品则分布在曲线上或与之相邻近。此研究结果得到了柴达木贝壳堤沉积物的REE数据的验证,运用此方法可以为直观的判别剖面中的不同沉积相,并为定量化划分地层提供依据。     

REE geochemistry of the recent playa sediments from the Thar Desert, India: An implication to playa sediment provenance

The playas (saline lakes) situated in the Thar Desert, north-west India, provide prominent examples of alkaline brine and varying assemblages of detrital and evaporite mineralogy. The eastern margin of the desert is relatively semi-arid, whereas the central to western region is arid to hyper-arid in nature. Rare earth elements (REEs) systematics in the sediments of nine different playas of the Thar Desert were studied to understand the provenance of the sediments and the intensity of chemical weathering in the region. Based on the REE patterns, fractionation of light REE (LREE) (La/Sm)_N and heavy REE (HREE) (Gd/Yb)_N, and Eu anomaly (Eu/Eu*), the upper continental crust normalised playa sediments are divided into two different groups. The eastern margin playa sediments show homogeneous REE contents, relatively positive Eu anomaly and depleted HREE values, whereas the western arid core playa sediments have highly variable REE contents, relatively negative Eu anomaly and similarly fractioned LREE and HREE patterns. The dissimilarity in the degree of HREE fractionations both in the eastern and western playa sediments is attributed to the differential distribution of minerals, depending upon their resistance to chemical weathering. It is believed that the relatively higher abundance of REE bearing heavy minerals and the presence of higher amounts of evaporites influence the large variation of REE distribution and enriched HREE in the western playa sediments. Apart from the relatively higher abundance of heavy minerals, the presence of rock fragments of variable petrographic character and roundness mirror the lower rock–water interaction in the arid western region. The presence of well-rounded metamorphic rock fragments and minerals, sourced from the eastern margin Aravalli mountains, indicates that the playas of the entire desert get the detrital and dissolved material mainly from the Aravalli mountains. Additionally, the western playas receive sediments from their surrounding Proterozoic and Mesozoic formations. This interpretation is supported by the presence of angular rock fragments of basalt, rhyolite and limestone in the western playas.     

Rare earth elements in ferromanganese nodules and other marine phases

The concentrations of rare-earth elements (REE) have been measured in 31 ferromanganese nodules from the Pacific and Indian Oceans and vary by almost a factor of 5. Too few nodules have been analyzed to define possible regional trends. The shale-normalized patterns, however, permit division of nodules into two groups: those from depth greater than 3000–3500 m and those from less depth. The factors that determine this change in the relative concentration of REE may be related to the mineralogy of manganese phases and/or the transport of REE to the deep ocean by particulate matter.Comparison of the REE patterns of nodules with those of phillipsite, phosphorite, clays, CaCO₃ and seawater suggests that the patterns of these phases reflect fractionation from an initial pattern closely resembling that of shale. By assuming that the accumulation rate of REE in clays, CaCO₃ and nodules is represented by that for surface sediments, it has been possible to estimate an accumulation rate of phillipsite in pelagic sediments of the Pacific of 0.02 mg/cm²/yr.     

Infiltration of refractory melts into the lowermost oceanic crust: evidence from dunite- and gabbro-hosted clinopyroxenes in the Bay of Islands Ophiolite

Up to 3 km of dunitic rocks occur below crustal gabbro in the Blow Me Down massif (Bay of Islands Ophiolite, Newfoundland). Analyses of dunite- and gabbro-hosted clinopyroxene grains (cpx) for rare earth elements (REE), Zr, and Ti reveal three types of chondrite-normalized patterns: N-group patterns are similar to cpx grains as they would form by fractionation from a range of mid ocean ridge basalts (MORB). They are typical for a few higher level dunitic samples as well as mafic cumulates. F-group patterns show light REE depletion, very strong middle REE fractionation and a positive Zr anomaly and occur in dunites only. R-group patterns are severely depleted in both light and heavy REEs relative to MORB-like cpx and two samples of the group display a positive Ti anomaly. They are also restricted to dunitic rocks. The patterns are explained in a two stage model in which an established dunite sequence, dominated by MORB-type cumulate signatures (N-group), was infiltrated by extremely refractory melts. During infiltration of the refractory melt chromatographic fractionation occurred, transforming N-group dunites into F-group and R-group dunites. The F-group patterns are composite patterns: heavy REE, Ti ± Zr reflect the original MORB-like cumulate dunite host, light REEs indicate equilibrium with the infiltrating, refractory melts. Steep slopes in the middle REEs reflect the position of the chromatographic front. For more intense percolation of refractory melts, R-group patterns with a positive Ti anomaly will form by the same process. The rest of the R-group patterns displaying no positive Ti anomaly may represent either the most intensely reacted host rocks or these dunites derive directly as cumulates from refractory melts. Only small volumes of refractory melt (a 5 m column) are required to imprint the observed trace element pattern on the thick original dunite sequence. One of several possible origins for the refractory melts is transformation of original MORB-type melts by way of chromatographic fractionation within the highly depleted, residual uppermost mantle. In the framework of an oceanic spreading centre, the migrating, refractory liquids are considered a late event following the main constructive stage dominated by aggregated melts. The study demonstrates that highly refractory melts can exist under oceanic spreading centres dominated by a MORB-like cumulate and volcanic sequence. Received: 2 September 1996 / Accepted: 20 November 1997     

Phosphorus Cycle in the Ocean

The behavior of phosphorus is considered at major stages of the sedimentary cycle beginning with supply sources for its delivery into the ocean to precipitation and its sedimentation, localization and subsequent diagenetic redistribution in bottom sediments. River runoff represents the main phosphorus source in the ocean. It delivers annually about 1.5 Mt of dissolved phosphorus and more than 20 Mt of suspended phosphorus into the ocean. Up to 80% of the suspended phosphorus incorporated in the lithogenic material precipitates within submarine continental margins. Phosphorus dissolved in seawater repeatedly participates in biogeochemical processes owing to its assimilation by phytoplankton that annually consumes from 1.5 to 2.5 Gt of phosphorus. Dissolved phosphorus is incorporated in organic remains and precipitates from seawater by a biogenic mechanism, too. Only a part of phosphorus settled onto the bottom is buried in sediments. Due to reducing diagenetic processes, up to 30–40% of the primarily precipitated phosphorus diffuses from the upper layer of sediments into bottom water. Diffusion flux into the ocean significantly exceeds the supply of dissolved phosphorus from river runoff. The absolute mass phosphorus dispersed in sediments is several orders of magnitude greater than the mass concentrated in phosphorite deposits. However, the majority of phosphorite formation epochs coincide with the intensification of total phosphorus accumulation in marine sediments in conditions of humid climate, intense chemical weathering of rocks on continents, and considerable expansion of the oceanic shelf area.     

Geochemical constraints on the late-stage evolution of basaltic magma as revealed by composite dikes within the Kangâmiut dike swarm, West Greenland

The Kangâmiut dike swarm in West Greenland contains numerous composite dikes with mafic margins and andesitic centers. Internal chilled margins show that the andesitic centers intruded into the middle of the mafic dikes. Major element systematics indicate that the fractionation of olivine, clinopyroxene, plagioclase and Fe–Ti oxides drove the evolution of the Kangâmiut parental magma during its transition from mafic to andesitic compositions. Incompatible trace elements show a marked relative decrease in middle and heavy rare-earth elements (REE) between the mafic margins and the andesitic centers. The decrease in the REE is not explicable by olivine, clinopyroxene, plagioclase and Fe–Ti oxide fractionation or by the fractionation of the accessory phases apatite, zircon or garnet. Rb–Sr and Sm–Nd isotopes from margin and center pairs from these composite dikes are nearly identical indicating that crustal contamination had little to no affect on their evolution. Trace element modeling utilizing the mixing of evolved Kangâmiut magmas and low degree melts derived from partial melting of garnet lherzolite produce excellent fits with the trace element patterns for the andesitic centers. These models suggest that the late-stage evolution of the Kangâmiut dikes included input of mantle melts produced during the end stages of rifting.     

Submarine groundwater discharge is an important net source of light and middle REEs to coastal waters of the Indian River Lagoon, Florida, USA

Porewater (i.e., groundwater) samples were collected from multi-level piezometers across the freshwater-saltwater seepage face within the Indian River Lagoon subterranean estuary along Florida’s (USA) Atlantic coast for analysis of the rare earth elements (REE). Surface water samples for REE analysis were also collected from the water column of the Indian River Lagoon as well as two local rivers (Eau Gallie River, Crane Creek) that flow into the lagoon within the study area. Concentrations of REEs in porewaters from the subterranean estuary are 10-100 times higher than typical seawater values (e.g., Nd ranges from 217 to 2409 pmol kg⁻¹), with submarine groundwater discharge (SGD) at the freshwater-saltwater seepage face exhibiting the highest REE concentrations. The elevated REE concentrations for SGD at the seepage face are too high to be the result of simple, binary mixing between a seawater end-member and local terrestrial SGD. Instead, the high REE concentrations indicate that geochemical reactions occurring within the subterranean estuary contribute substantially to the REE cycle. A simple mass balance model is used to investigate the cycling of REEs in the Indian River Lagoon and its underlying subterranean estuary. Mass balance modeling reveals that the Indian River Lagoon is approximately at steady-state with respect to the REE fluxes into and out of the lagoon. However, the subterranean estuary is not at steady-state with respect to the REE fluxes. Specifically, the model suggests that the SGD Nd flux, for example, exported from the subterranean estuary to the overlying lagoon waters exceeds the combined input to the subterranean estuary from terrestrial SGD and recirculating marine SGD by, on average, ∼100 mmol day⁻¹. The mass balance model also reveals that the subterranean estuary is a net source of light REEs (LREE) and middle REEs (MREE) to the overlying lagoon waters, but acts as a sink for the heavy REEs (HREE). Geochemical modeling and statistical analysis further suggests that this fractionation occurs, in part, due to the coupling between REE cycling and iron redox cycling within the Indian River Lagoon subterranean estuary. The net SGD flux of Nd to the Indian River Lagoon is ∼7-fold larger than the local effective river flux to these coastal waters. This previously unrecognized source of Nd to the coastal ocean could conceivably be important to the global oceanic Nd budget, and help to resolve the oceanic “Nd paradox” by accounting for a substantial fraction of the hypothesized missing Nd flux to the ocean.     

Geochemical and mineralogical characteristics of recent clastic sediments from lower Godavari river: Implications of source rock weathering

The major, trace and rare earth elements geochemistry and clay mineral compositions in the river bed sediments from lower reaches of Godavari river suggest that they are derived from weathering of felsic rocks. Trace and rare earth elemental compositions indicate evidence of sedimentary sorting during transportation and deposition. Lower concentrations of transition elements, such as V, Ni and Cr imply enrichment of felsic minerals in these bed sediments. The REE pattern in lower Godavari sediments is influenced by the degree of source rock weathering. The light rare earth elements (LREE) content are indicating greater fractionation compared to the heavy rare earth elements (HREE). A striking relationship is observed between TiO₂ and gZREE content suggesting a strong control by LREE-enriched titaniferous minerals on REE chemistry. Shale-normalized REE pattern demonstrate a positive Eu anomaly, suggesting weathering of feldspar and their secondary products, which are enriched in Eu. Chondrite-normalised REE pattern is characteristic of felsic volcanic, granites and gnessic source rocks. Trace elemental compositions in sediments located near urban areas suggest influence of anthropogenic activity. Chemical Index of Alteration (CIA) is high (avg. 65.76), suggesting a moderate chemical weathering environment. X-ray diffraction analysis of clay fraction shows predominance of clay minerals that are formed because of the chemical weathering of felsic rocks.     

Geodynamic significance of the Raspas Metamorphic Complex (SW Ecuador): geochemical and isotopic constraints

The Raspas Metamorphic Complex of southwestern Ecuador is regarded as the southernmost remnant of oceanic and continental terranes accreted in the latest Jurassic–Early Cretaceous. It consists of variably metamorphosed rock types. (1) Mafic and ultramafic rocks metamorphosed under high-pressure (HP) conditions (eclogite facies) show oceanic plateau affinities with flat REE chondrite-normalized patterns, Nd_{150 Ma} ranging from +4.6 to 9.8 and initial Pb isotopic ratios intermediate between MORB and OIB. (2) Sedimentary rocks metamorphosed under eclogitic conditions exhibit LREE enriched patterns, strong negative Eu anomalies, Rb, Nb, U, Th, Pb enrichments, low Nd_{150 Ma} values (from −6.4 to −9.5), and high initial ⁸⁷Sr/⁸⁶Sr and ^206,207,208Pb/²⁰⁴Pb isotopic ratios suggesting they were originally sediments derived from the erosion of an old continental crust. (3) Epidote-bearing amphibolites show N-MORB affinities with LREE depleted patterns, LILE, Zr, Hf and Th depletion, high Nd_{150 Ma} (>+10) and low initial Pb isotopic ratios.The present-day well defined internal structure of the Raspas Metamorphic Complex seems to be inconsistent with the formerly proposed interpretation of a “tectonic mélange”. The association of oceanic plateau rocks and continent-derived sediments both metamorphosed in HP conditions suggests that the thin edge of the oceanic plateau first entered the subduction zone and dragged sediments downward of the accretionary wedge along the Wadatti–Benioff zone. Subsequently, when its thickest part arrived into the subduction zone, the oceanic plateau jammed the subduction processes, due to its high buoyancy.In Ecuador and Colombia, the latest Jurassic–Early Cretaceous suture involves HP oceanic plateau rocks and N-MORB rocks metamorphosed under lower grades, suggesting a composite or polyphase nature for the latest Jurassic–Early Cretaceous accretionary event.     

A study of differentiation pattern and rare earth elements migration in geochemical and hydrogeochemical environments of Airekan and Cheshmeh Shotori areas (Central Iran)

The Airekan and Cheshmeh Shotori areas are located about 60 km northeast of Khour, in Isfahan province from Central Iran. Research on characteristics and rare earth elements (REE) pattern in hydrogeochemical environments of these areas suggests the same origin for the elements dissolved in groundwater in these areas. Investigation of migration pattern of REE in hydrogeochemical environments shows that the migration and transportation of REE has occurred through chloride complexes. REEs, leached by water/rock interaction from the Airekan granite, are transported by groundwater and then precipitated in the Cheshmeh Shotori area. Study of the Cheshmeh Shotori sediments shows the presence of a sequence of red oxidized and dark layers. Geochemical characteristics of these sediments reveal that their REE characteristics are mainly inherited from the Airekan granite. Changes in the REE pattern of these sediments with depth show that changes in oxidation and reduction process have not played a significant role in controlling their behavior. It is crucial to note that adsorption of REEs dissolved in water by hydrosilicate increases these elements in depth. The REE behavior shows water/rock interaction between the granitic rocks and groundwater as the main factor of solution, migration and precipitation of REEs in the Cheshmeh Shotori area.     

Trace element concentrations in silicate spherules from oceanic sediments

The possible existence of meteoritic spherules was investigated among several silicate spherules separated from oceanic sediments and analyzed by means of INAA (instrumental neutron activation analysis).A 0.72 mg glassy spherule was found to have uniform enrichment of 4 ~ 5 for the refractory REE (rare earth elements) and Sc with substantial depletion of Ce relative to chondritic abundances. This implies that this spherule is meteoritic in origin and that the enrichment of refractory elements was established by high temperature heating in a high O/H environment, possibly at the time of entering the Earth's atmosphere.The other three analyzed spherules showed major and trace element abundances that are consistent with an origin in the oceanic environment.     

三江地区中段地球化学省初探

三江中段可划分为(亲)扬子地球化学省与(亲)冈瓦纳地球化学省.前者上地幔岩有方辉橄榄岩和二辉橄榄岩,幔型元素(KT)富集,REE呈平坦&弱富集型;大洋火山岩以基性岩\亚碱性\洋脊型为主;铅同位素     

The Stream Sediment Geochemistry of the Walawe Ganga Basin of Sri Lanka - Implications for Gondwana Mineralization

A regional geochemical and mineralogical study aimed at investigating the mineralization in the western-part of the Walawe Ganga (river) Basin in Sri Lanka is represented in this paper. The river basin is the 3^rd largest in the country and has within it a boundary zone between two geologically different crustal blocks, which are marked by granulitic grade rocks and amphibolite grade rocks. Size fractions of stream sediments (< 63 μm; 63–125 μm; 125–177 μm and 177–250 μm) developed on the granulite-grade metamorphic terrain have been analysed at their source for their mineralogical and selected element compositions. Thirty-eight (38) sediment samples and 15 representative probable parent rock samples were chemically analysed giving special emphasis to the High Field Strength trace Elements (HFSE) including the Rare Earth Elements (REE). The granulite grade rocks in the study area is geochemically similar to that of post Archean upper crust. However the stream sediments developed from the high-grade rocks during the intense weathering, are markedly enriched with HFSE and REE. The enrichment of HFSE and LREE is accounted for by the presence of HFSE- and REE- rich accessory mineral phases such as zircon, monazite, apatite, garnet and rutile in the sediments. In some samples, the content of heavy minerals contributes as much as 50 wt. %. These minerals act as a source of elements in the sediments. However, extreme hydraulic sorting of HFSE- and REE-bearing minerals during the sediment deposition cannot be expected within a short distance from near the sources except from a mineralized occurrence. Therefore, the higher enrichment of these elements presumably indicates occurrences of scattered mineral sources such as highly differentiated granites and associated pegmatites within the Walawe Ganga drainage basin. These granitic pegmatites are probably intruded during or soon after the main granulite-facies metamorphic event and similar events are seen in other terrains of East-Gondwana.     

Geochemistry of highly-undersaturated ocean island basalt suites from the South Atlantic Ocean: Fernando de Noronha and Trindade islands

The volcanic rocks of the South Atlantic Ocean islands of Fernando de Noronha and Trindade comprise a diverse magmatic series ranging from nephelinites and basanites to phonolites and, on Fernando de Noronha, trachytes. All rock types are highly silica undersaturated with the exception of Fernando de Noronha trachytes_, and have high abundances of incompatible trace elements and strongly LREE (light rare earth element)-enriched REE patterns. Crystal fractionation of parental basanitic magmas produced evolved phonolites and trachytes which display severe trace-element fractionation, even among trace elements (Nb, Ta, Zr, Hf) which normally behave highly incompatibly during crystallisation of alkaline magmas. Moderately to highly evolved compositions develop strongly MREE (middle REE)-depleted REE patterns, and become increasingly depleted in elements such as Nb and, in particular, Ta. Ratios of Nb/Ta and Zr/Hf are highly fractionated in phonolites (60–65, 64–77 respectively in Fernando de Noronha phonolites) compared to ratios in basanites (14, 45 respectively). The compatibility of Nb, Ta, and the REE, and the strong fractionation of Nb/Ta and Zr/Hf ratios and the MREE, during crystallisation from basanite to phonolite are attributable to the crystallisation of small amounts (<5%) of sphene. Trace-element behaviour is relatively insensitive to the major phenocryst phases, and is controlled by minor phases in highly undersaturated alkaline suites. Incompatible trace-element ratios (e.g. La/Nb, Th/Ta) in nephelinites and basanites from Fernando de Noronha and Trindade are generally comparable with those in basaltic and hawaiitic OIB (ocean island basalt) lavas from other South Atlantic islands, but are distinct from those of Gough and Tristan da Cunha OIB. The mantle source for the highly undersaturated volcanism on Fernando de Noronha and Trindade is similar in trace-element characteristics to the typical OIB source which produces alkaline lavas with significant relative enrichment in Nb and Ta compared to other trace elements (as expressed by low La/Nb, Ba/Nb and Th/Ta ratios). The highly undersaturated nature of the magmas and the slight fractionation of some incompatible-element ratios (elevated Ba/Nb, Ba/Rb, Ba/Th etc.) is consistent with a smaller degree of melting of a typical OIB source, but with residual phlogopite in the source to account for significant K depletion and LIL-element fractionation.