Negative cerium anomalies in the saprolite zone of serpentinite lateritic profiles in the Lomié ultramafic complex,South-East Cameroon

Strong negative cerium anomalies are developed in the saprolite zone of two serpentinite lateritic profiles in the Mada region of the Kongo–Nkamouma massif in the Lomié ultramafic complex (South-East Cameroon).The total lanthanide contents increase strongly from the parent rock (1.328 ppm) to the weathered materials (ranging from 74.32 to 742.18 ppm); the highest value is observed in the black nodules from the western weathering profile and the lowest one in the top of the clayey surface soil from the same profile. The lanthanide contents, except cerium, are highest in the saprolite and decrease along the profile. The light REE contents are very high compared to those of the heavy REE (LREE/HREE ranging from 3.21 to 44.37). The lanthanides normalized with respect to the parent rock reveal: (i) strong negative Ce anomalies with [Ce/Ce¹] ranging from 0.006 to 0.680 in the saprolite zone; (ii) strong positive Ce anomalies with [Ce/Ce¹] ranging from 1.23 to 23.96 from the top of the saprolite to the clayey surface horizon; (iii) positive Eu anomalies with [Eu/Eu¹] ranging from 2.09 to 2.41 in all the weathered materials.Mass balance evaluation shows that, except cerium, lanthanides have been highly accumulated in the saprolite zone and moderately concentrated in the upper part of both profiles. Cerium has been highly accumulated in the nodules of the West Mada profile. The presence of negative Ce anomalies is confirmed by its low degree of accumulation whereas the positive ones are related to its high degree of accumulation.     

Platinum-group element abundances in the upper mantle: new constraints from in situ and whole-rock analyses of Massif Central xenoliths (France)

Fourteen peridotite xenoliths collected in the Massif Central neogene volcanic province (France) have been analyzed for platinum-group elements (PGE), Au, Cu, S, and Se. Their total PGE contents range between 3 and 30 ppb and their PGE relative abundances from 0.01 to 0.001 × CI-chondrites, respectively. Positive correlations between total PGE contents and Se suggest that all of the PGE are hosted mainly in base metal sulfides (monosulfide solid solution [Mss], pentlandite, and Cu-rich sulfides [chalcopyrite/isocubanite]). Laser ablation microprobe-inductively coupled plasma mass spectrometry analyses support this conclusion while suggesting that, as observed in experiments on the Cu-Fe-Ni-S system, the Mss preferentially accommodate refractory PGEs (Os, Ir, Ru, and Rh) and Cu-rich sulfides concentrate Pd and Au. Poikiloblastic peridotites pervasively percolated by large silicate melt fractions at high temperature (1200°C) display the lowest Se (<2.3 ppb) and the lowest PGE contents (0.001 × CI-chondrites). In these rocks, the total PGE budget inherited from the primitive mantle was reduced by 80%, probably because intergranular sulfides were completely removed by the silicate melt. In contrast, protogranular peridotites metasomatized by small fractions of volatile-rich melts are enriched in Pt, Pd, and Au and display suprachondritic Pd/Ir ratios (1.9). The palladium-group PGE (PPGE) enrichment is consistent with precipitation of Cu-Ni-rich sulfides from the metasomatic melts. In spite of strong light rare earth element (LREE) enrichments (Ce/Yb_N < 10), the three harzburgites analyzed still display chondrite-normalized PGE patterns typical of partial melting residues, i.e., depleted in Pd and Pt relative to Ir and Ru. Likewise, coarse-granular lherzolites, a common rock type in Massif Central xenoliths, display Pd/Ir, Ru/Ir, Rh/Ir, and Pt/Ir within the 15% uncertainty range of chondritic meteorites. These rocks do not contradict the late-veneer hypothesis that ascribes the PGE budget of the Earth to a late-accreting chondritic component; however, speculations about this component from the Pd/Ir and Pt/Ir ratios of basalt-borne xenoliths may be premature.     

Behaviour of REE and mass balance calculations in a lateritic profile over chlorite schists in South Cameroon

An in situ weathering profile overlying chlorite schists in the Mbalmayo-Bengbis formations (South Cameroon) was chosen for the study of the behaviour of REE and the evaluation of geochemical mass balance. After physical and mineralogical studies, the chlorite schists and the undisturbed weathered materials were chemically analyzed for major elements (X-ray fluorescence and titrimetry) and REE (ICP-MS). The behaviour of the REE in the Mbalmayo weathering system was established in comparison with the REE of the reference parent rock. Mass balance calculations were applied to both major elements and REE. The mineralogy of the materials was determined with the aid of a Philips 1720, diffractometer. The chlorite schists of the Mbalmayo sector show low REE contents (Σ=153.44 ppm). These rocks are relatively rich in LREE (about 125 times the chondritic value) and relatively poor in HREE (about 20 times the chondritic value). The REE diagram normalized to chondrites shows a slightly split graph ((La/Yb)_N=6.18) with marked enrichment in LREE (LREE/HREE=9.50) in relation to HREE. Moreover, these spectra do not present any Ce anomaly, but a slightly positive Eu anomaly. The imperfectly evolved profile, whose materials are genetically linked, shows an atypical behaviour of REE. In effect, the LREE are more mobile than the HREE during weathering ((La/Yb)NASC<1) with weak Ce anomalies. This has been rarely reported in lateritic profiles characterized by higher HREE mobility than LREE during weathering processes with high Ce anomalies. This is either due to the difference in the stability of REE-bearing minerals, or to the weak acidic to basic pH conditions (6.70<pH<7.80), or even due to the average evolution of the weathering materials. The pathway of the REE along the profile is as follows: (1) leaching in the saprolites and summit of the profile, except for Ce, which precipitates very weakly in the nodular materials and the coarse saprolite materials, (2) at the base of the profile, solutions come in contact with chlorite schist formations, at this level, the pH increases (pH=7.79), HREE and a part of LREE partially void of Ce precipitate and (3) the other part of LREE precipitates further up in the profile. The geochemical mass balance calculations reveal that these elements are leached in the same phases as the relatively high Si, Al, K and Fe²⁺ contents.     

Platinum-group elements in the serpentinite lateritic mantles of the Kongo–Nkamouna ultramafic massif (Lomié region,South-East Cameroon)

The behaviour of PGE in a rainforest ecosystem were investigated in four lateritic profiles (Nkamouna, Napene, West and East Mada) developed on serpentinites in the Kongo–Nkamouna massif (Lomié region, South-East Cameroon). In serpentinites, the total PGE content attains 22 ppb whilst it ranges between 26 and 200 ppb in the weathering blanket. Amongst the analyzed elements (platinum, iridium, ruthenium, rhodium, palladium), platinum and ruthenium contents are high in the saprolite zone and in the hardened materials of some weathering profiles (40–66 ppb for platinum, 50–71 ppb for ruthenium). Apart from the hardened materials, the total PGE content decreases from the coarse saprolite towards the clayey surface soil. The Fe₂O₃-PGE diagram indicates a relatively similar behaviour in these iron-rich samples. The Pt–Ir, Pt–Pd, Pt–Ru, Pt–Rh diagrams portray positive correlations between platinum and other PGE. This fact is supported by the positive correlation noticed between IPGE and PPGE. The Pt/Ir, Pt/Pd, Pt/Ru and Pt/Rh values indicate that iridium, palladium, ruthenium and rhodium are more mobile than platinum. These data confirm the mobility of PGE in laterites and the positive correlation reveals that PGE might be accommodated in the interfaces of iron oxides. The mass balance assessment shows that PGE are strongly leached from the Kongo–Nkamouna weathering blanket except in the coarse saprolite of the Nkamouna profile.     

Geochemistry of Platinum Group and Rare Earth Elements of the Polymetallic Layer in the Lower Cambrian, Weng’an, Guizhou Province

Abstract: The black shales of the Lower Cambrian Niutitang Formation in Weng’an, on the Yangtze platform of south China, contain voluminous polymetallic sulfide deposits. A comprehensive geochemical investigation of trace, rare earth, and platinum group elements (PGE) has been undertaken in order to discuss its ore genesis and correlation with the tectono-depositional setting. The ore-bearing layers enrich molybdenum (Mo), nickel (Ni), vanadium (V), lead (Pb), strontium (Sr), barium (Ba) , uranium (U) , arsenic (As), and rare earth elements (REE) in abundance. High uranium/thorium (U/Th) ratios (U/Th>1) indicated that mineralization was mainly influenced by the hydrothermal process. The dU value was above 1.9, showing a reducing sedimentary condition. The REE patterns showed high enrichment in light rare earth elements (LREE) (heavy rare earth elements (HREE) (LREE/HREE=5–17), slightly negative europium (Eu) and cerium (Ce) anomalies (dEu=0.81–0.93), and positive Ce anomalies (dCe=0.76–1.12). PGE abundance was characterized by the PGE-type distribution patterns, enriching platinum (Pt), palladium (Pd), ruthenium (Ru) and osmium (Os). The Pt/Pd ratio was 0.8, which is close to the ratios of seawater and ultramafic rocks. All of these geochemical features suggest that the mineralization was triggered by hydrothermal activity in an extensional setting in the context of break-up of the Rodinian supercontinent.     

Origin of ultramafic xenoliths in high-Mg diorites from east-central China based on their oxidation state and abundance of platinum group elements

Ultramafic xenoliths are abundant in late Mesozoic high-Mg diorites at Laiwu, western Shandong Province; they are composed of dunite (>80 vol.%) with minor harzburgite (<10 vol.%) and olivine (Ol)-pyroxenite (<10 vol.%). We determined the abundance of siderophile and chalcophile elements of representative samples of xenoliths, and calculated oxidation conditions based on mineral chemistry. Bulk compositions of harzburgite show high Cr (2640–3430 ppm), Co (103–111 ppm), Ni (2210–2400 ppm), and high Ir-type platinum group elements (PGE) (IPGE, 14.0–17.8 ppb), with high ratios of IPGE to Pt-type PGE (PPGE, 3.1–6.3). Spinel contains moderate Cr (Cr# = 0.41–0.61). Our data suggest that the harzburgite is the residue of partial melting. The occurrence of orthopyroxene replacing Ol suggests that harzburgite was metasomatized by a Si-rich melt. Dunite contains high concentrations of Cr (> 3800 ppm), Co (>110 ppm), and Ni (>1680 ppm), and low concentrations of IPGE (<4.8 ppb), with low ratios of IPGE/PPGE (as low as 0.05), suggesting that dunite is the cumulate of a mafic melt. High Cr in chromite (Cr# > 0.7) and high Mg in Ol suggest that the parental melt was boninitic. Some Ol grains show variable, locally high Mg, up to Fo 94.3. We attribute these high values to the interaction of the Ol with abundant chromite in the cumulate. Both dunite and harzburgite indicate high log fO₂ values, ranging from fayalite-magnetite-quartz (FMQ) +1.4 to +2.4. The values contrast with fO₂ below that of the graphite–CO₂ buffer for xenoliths in early Palaeozoic diamondiferous kimberlite pipes in the area. The data indicate a sharp increase in fO₂ during Mesozoic time, likely caused by subduction of the Tethyan oceanic plate before collision with the Yangtze continent below the eastern margin of the North China craton.     

Geochemical study of peridotites from the Manipur Ophiolite Complex,Northeast India with special reference to their PGE concentration

The peridotites of the Manipur Ophiolite Complex (MOC) have been examined based on mineral chemistry, major elements and PGE contents. They represent high-magnesian cumulates with Mg# > 0.90 (Mg/Mg+Fe) in olivine and Cr# > 0.12 (Cr/Cr+Al) in spinel. High Mg* contents of the olivine show that these rocks are most likely derived from partial melting of the residual upper mantle. The peridotites contain higher concentration of Palladium Group PGE (PPGE) (Rh=4.4−6.6ppb; Pd=336−458ppb and Pt=14.6−36.4ppb) than the Iridium Group PGE (IPGE) (Os=2.4−5.8ppb; Ir=3.2−4.16ppb and Ru=5.2−7ppb). These are characterized by overall enrichment of PGE concentration (σPGE=365.8 − 516.6 ppb) and high ratio of (Pt+Pd)/(Os+Ir+Ru). This suggests that the rocks are formed by partial melting and crystal fractionation of olivine-rich (picritic) magma.     

Trace elemental and PGE geochemical constraints of Mesozoic and Cenozoic peridotitic xenoliths on lithospheric evolution of the North China Craton

Whole-rock major, trace, and platinum-group elemental (PGE) data, and major and trace element compositions of diopsides are reported for peridotite xenoliths from (1) early Mesozoic volcanic breccias in Xinyang, located at the southern margin of the North China Craton, and (2) Cenozoic basalts in Hebi and Shanwang, both of which are situated within the craton and lie on the North-South Gravity Line and the Tanlu fault zone, respectively. The early Mesozoic Xinyang xenoliths are harzburgites containing <2% Cpx with high Cr^# and enriched in LREE but depleted in HFSE. These xenoliths have chondritic Pd/Ir (1.9-6.6) and Ru/Ir (3.5-4.0) ratios and high Ni and low CaO, Al₂O₃, and S contents, indicating derivation from a highly refractory mantle that experienced carbonatitic metasomatism. Negative Ce (mean δCe = 0.50) and low Mg/Si ratios of the Xinyang peridotites record the addition of crustal components likely produced from subducted continental material of the Yangtze Craton in the early Mesozoic. The subduction-related modification of the lithospheric mantle was limited to the area close to the collision zone rather than being pervasive throughout the craton. The Cenozoic Hebi peridotite xenoliths are harzburgites with ≤4.5% Cpx and have low CaO and Al₂O₃ but high Ni contents, chondritic Ru/Ir ratios (2.5-5.4), and a wide range of CaO/Al₂O₃, Na₂O/TiO₂, Pt/Ir (0.4-2.3), and Pd/Pt (1.1-8.5) ratios. These peridotites are interpreted as the shallow relics of the cratonic mantle. In contrast, the Cenozoic Shanwang xenoliths are lherzolites (5.6%-19.5% Cpx), which have low Ni contents and low Ni/Cu and Mg/Si ratios, but high CaO, Al₂O₃, S, and HREE contents, and relatively high Ru/Ir and Pd/Ir ratios. The Shanwang peridotites show pronounced positive Ti and Sr, negative Th, and slightly negative Y, Zr, and Hf anomalies. They are believed to represent newly accreted fertile lithospheric mantle derived from cooling of upwelling asthenosphere. The documented temporal and spatial variations in the Mesozoic-Cenozoic mantle support the previous suggestion that the buoyant refractory continental keel in the eastern part of the North China Craton was heterogeneously replaced by younger fertile lithospheric mantle in the late Cretaceous-early Tertiary.     

Sulfur and selenium systematics of the subcontinental lithospheric mantle: Inferences from the Massif Central xenolith suite (France)

Selenium has been analyzed in addition to S in 58 spinel peridotite xenoliths collected in Cenozoic alkali basalts from the Massif Central (France). The S concentration range now available for this suite, calculated from 123 samples, is the largest ever reported for alkali basalt-hosted xenoliths (<3-592 ppm). Likewise, the Se concentrations range between 0.2 and 67 ppb. No partial melting signature can be identified from the S and Se systematic. Half of the analyzed xenoliths have lost S during supergene weathering. By contrast, neither surficial alteration, nor loss of chalcophile elements during eruption can explain the regional-scale variations of S and Se concentrations. A first group of lherzolite xenoliths sampled in Southern Massif Central, from volcanic centers older and spatially unrelated to the Massif Central plume that triggered the Cenozoic volcanism, contains between 20 and 250 ppm S (with occasional S concentrations up to 592 ppm) and 12-67 ppb Se. It is clear that the highest S values, originally interpreted as representing S abundances in the primitive mantle, were in fact enriched by metasomatism. Highly variable S and Se contents (<5-360 ppm; 9-52 ppb) have also been observed in peridotite xenoliths collected in the Northern Massif Central, from volcanic centers mostly older than the plume. Like Group I xenoliths, these Group II xenoliths were strongly metasomatized by volatile-rich carbonated/silicated melts which precipitated Cu-rich sulfides. A third group of xenoliths from Plio-Quaternary basalts spatially related to the Massif Central Plume are uniformly poor in S (10-60 ppm) and Se (9-29 ppb). In this Group III, poikiloblastic textured xenoliths have lost most of their S and Se budget by peridotite-melt interactions at high melt/rock ratios. Taken as a whole, the Massif Central xenolith suite provides further evidence for strong heterogeneities in the S and Se budget of the sub-continental lithospheric mantle. However, the few LREE-depleted fertile lherzolites that escaped strong metasomatic alterations suggest a S- and Se-depleted primitive mantle reservoir compared to currently accepted primitive mantle estimates.     

Platinum-Group Element Geochemical Characteristics of the Picrites and High-Ti Basalts in the Binchuan Area,Yunnan Province

The Binchuan area of Yunnan is located in the western part of the Emeishan large igneous province in the western margin of the Yangtze Block.In the present study,the Wuguiqing profile in thickness of about 1440 m is mainly composed of high-Ti basalts,with minor picrites in the lower part and andesites,trachytes,and rhyolites in the upper part.The picrites have relatively higher platinum-group element（PGE） contents（ΣPGE=16.3-28.2 ppb）,with high Cu/Zr and Pd/Zr ratios,and low S contents（5.03-16.9 ppm）,indicating the parental magma is S-unsaturated and generated by high degree of partial melting of the Emeishan large igneous province（ELIP） mantle source.The slightly high Cu/Pd ratios（11 000-24 000） relative to that of the primitive mantle suggest that 0.007%sulfides have been retained in the mantle source.The PGE contents of the high-Ti basalts exhibit a wider range（ΣPGE=0.517-30.8 ppb）.The samples in the middle and upper parts are depleted in PGE and haveε_Nd（260 Ma） ratios ranging from -2.8 to -2.2,suggesting that crustal contamination of the parental magma during ascent triggered sulfur saturation and segregation of about 0.446%-0.554% sulfides,and the sulfide segregation process may also provide the ore-forming material for the magmatic Cu-Ni-PGE sulfide deposits close to the studied basalts.The samples in this area show Pt-Pd type primitive mantle-normalized PGE patterns,and the Pd/Ir ratios are higher than that of the primitive mantle（Pd/Ir=1）,indicating that the obvious differentiation between Ir-group platinum-group elements（IPGE） and Pd-group platinum-group elements（PPGE） are mainly controlled by olivine or chromites fractionation during magma evolution.The Pd/Pt ratios of most samples are higher than the average ratio of mantle（Pd/Pt=0.55）,showing that the differentiation happened between Pt and Pd.The differentiation in picrites may be relevant to Pt hosted in discrete refractory Pt-alloy phase in the mantle;whereas the differentiation in the high-Ti basalts is probably associated with the fractionation of Fe-Pt alloys,coprecipitating with Ir-Ru-Os alloys.Some high-Ti basalt samples exhibit negative Ru anomalies,possibly due to removal of laurite collected by the early crystallized chromites.     

Geochemistry of Platinum Group and Rare Earth Elements of the Polymetallic Layer in the Lower Cambrian,Weng'an,Guizhou Province

The black shales of the Lower Cambrian Niutitang Formation in Weng'an.on the Yangtze platform of south China,contain voluminous polymetallic sulfide deposits.A comprehensive geochemical investigation of trace,rare earth,and platinum group elements(PGE)has been undertaken in order to discuss its ore genesis and correlation with the tectono.depositional setting.The ore-bearing layers enrich molybdenum(Mo),nickeI(Ni),vanadium(V),lead(Pb),strontium(Sr), bariam(Ba),uranium(U),arsenic(As),and rare earth elements(REE)in abundance.High uranium/thorium(U/Th)ratios(U/Th>1)indicated that mineralization was mainly influenced by the hydrothermal process.The δU value Was above 1.9.showing a reducing sedimentary condition.The REE patterns showed high enrichment in Iight rare earth elements (LREE)(heavy rare earth elements (HREE)(LREE/HREE=5-17),slightly negative europium(EU)and cerium(Ce)anomalies(δEu=0.81-0.93).and positive Ce anomalies(δCe=0.76-1.12).PGE abundance was characterized by the PGE-type distribution patterns,enriching platinum(Pt),palladium(Pd),ruthenium(RuJ and osmium(Os).The Pt,Pd ratio was 0.8.which is close to the ratios of seawater and ultramafic rocks.AII of these geochemical features suggest that the mineralization was triggered by hydrothermal activity in an extensionai setting in the context of break-up of the Rodinian supercontinent.     

Rare earth element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (⁸⁷Sr/⁸⁶Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]_PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]_PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]_PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] _PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]_PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The ⁸⁷Sr/⁸⁶Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.     

Mobilization and redistribution of major and trace elements in two weathering profiles developed on serpentinites in the Lomié ultramafic complex, South-East Cameroon

The behaviour of major and trace elements have been studied along two serpentinite weathering profiles located in the Kongo-Nkamouna and Mang North sites of the Lomié ultramafic complex.The serpentinites are characterized by high SiO₂ and MgO contents, very low trace, rare earth and platinum-group element contents. Lanthanide and PGE contents are higher in the Nkamouna sample than in Mang North. Normalized REE patterns according to the CI chondrites reveal that: (i) all REE are below chondrites abundances in the Mang North sample; (ii) the (La/Yb)_N ratio value is higher in the Nkamouna sample (23.72) than in the Mang one (1.78), this confirms the slightly more weathered nature of the Nkamouna sample. Normalized PGE patterns according to the same CI chondrites reveal a negative Pt anomaly in the Mang sample. The Nkamouna sample is characterized by a flat normalized PGE pattern.All element contents increase highly from the parent rock to the coarse saprolite.In the weathering profiles, Fe₂O₃ contents decrease from the bottom to the top contrarily to Al₂O₃, SiO₂ and TiO₂. The contents of alkali and alkaline oxides are under detection limit.Concerning trace elements, Cr, Ni, Co, Cu, Zn and Sc decrease considerably from the bottom to the top while Zr, Th, U, Be, Sb, Sn, W, Ta, Sr, Rb, Hf, Y, Li, Ga, Nb and Pb increase towards the clayey surface soil. Chromium, Ni and Co contents are high in the weathered materials in particular in the saprolite zone and in the nodules.REE contents are high in the weathered materials, particularly in Nkamouna. Their concentrations decrease along both profiles. Light REE are more abundant than heavy REE. Normalized REE patterns according to the parent rock reveal positive Ce anomalies in all the weathered materials and negative Eu anomalies only at the bottom of the coarse saprolite (Nkamouna site). Positive Ce anomalies are higher in the nodular horizon of both profiles. An additional calculation method of lanthanide anomalies, using NASC data, confirms positive Ce anomalies ([Ce/Ce^*]_NASC = 1.15 to 60.68) in several weathered materials except in nodules ([Ce/Ce^*]_NASC = 0.76) of the upper nodular horizon (Nkamouna profile). The (La/Yb)_N ratios values are lower in the Nkamouna profile than in Mang site.PGE are more abundant in the weathered materials than in the parent rock. The highest contents are obtained in the coarse saprolite and in the nodules. The elements with high contents along both profiles are Pt (63–70 ppb), Ru (49–52 ppb) and Ir (41 ppb). Normalized PGE patterns show positive Pt anomalies and negative Ru anomalies.The mass balance evaluation, using thorium as immobile element, reveals that:

– major elements have been depleted along the weathering profile, except for Fe, Mn and Ti that have been enriched even only in the coarse saprolite;

– all the trace elements have been depleted along both profiles, except for Cr, Co, Zn, Sc, Cu, Ba, Y, Ga, U and Nb that have been enriched in the coarse saprolite;

– rare earth elements have been abundantly accumulated in the coarse saprolite, before their depletion towards the top of the profiles;

– platinum-group elements have been abundantly accumulated in the coarse saprolite but have been depleted towards the clayey surface soil.

Moreover, from a pedogenetical point of view, this study shows that the weathering profiles are autochtonous, except in the upper part of the soils where some allochtonous materials are revealed by the presence of zircon grains.     

Geochemical and mineralogical characteristics of ion-adsorption type REE mineralization in Phuket, Thailand

Geochemical and mineralogical studies were conducted on the 12-m-thick weathering profile of the Kata Beach granite in Phuket, Thailand, in order to reveal the transport and adsorption of rare earth elements (REE) related to the ion-adsorption type mineralization. The parent rock is ilmenite-series biotite granite with transitional characteristics from I type to S type, abundant in REE (592 ppm). REE are contained dominantly in fluorocarbonate as well as in allanite, titanite, apatite, and zircon. The chondrite-normalized REE pattern of the parent granite indicates enrichment of LREE relative to HREE and no significant Ce anomaly. The upper part of the weathering profile from the surface to 4.5 m depth is mostly characterized by positive Ce anomaly, showing lower REE contents ranging from 174 to 548 ppm and lower percentages of adsorbed REE from 34% to 68% compared with the parent granite. In contrast, the lower part of the profile from 4.5 to 12 m depth is characterized by negative Ce anomaly, showing higher REE contents ranging from 578 to 1,084 ppm and higher percentages from 53% to 85%. The negative Ce anomaly and enrichment of REE in the lower part of the profile suggest that acidic soil water in an oxidizing condition in the upper part mostly immobilized Ce⁴⁺ as CeO₂ and transported REE³⁺ downward to the lower part of the profile. The transported REE³⁺ were adsorbed onto weathering products or distributed to secondary minerals such as rhabdophane. The immobilization of REE results from the increase of pH due to the contact with higher pH groundwater. Since the majority of REE in the weathered granite are present in the ion-adsorption fraction with negative Ce anomaly, the percentages of adsorbed REE are positively correlated with the whole-rock negative Ce anomaly. The result of this study suggests that the ion-adsorption type REE mineralization is identified by the occurrence of easily soluble REE fluorocarbonate and whole-rock negative Ce anomaly of weathered granite. Although fractionation of REE in weathered granite is controlled by the occurrence of REE-bearing minerals and adsorption by weathering products, the ion-adsorption fraction tends to be enriched in LREE relative to weathered granite.     

渝东南下寒武统黑色岩系稀土元素地球化学特征与沉积环境

渝东南及周边地区下寒武统黑色岩系稀土总量略低于北美页岩,∑LREE/∑HREE值为1.99～9.01,平均6.86,轻稀土相对富集;δEu值为0.69～7.33,平均2.79;δCe值为0.70～1.01,平均0.85。区内下寒武统黑色岩系为正常海水与热水沉积作用的混合产物,形成于缺氧还原环境逐渐向弱氧化环境过渡的外陆架。     

羌塘盆地那底岗日地区布曲组碳酸盐岩烃源岩稀土元素分布特征及意义

对采自羌塘盆地那底岗日地区布曲组碳酸盐岩烃源岩进行了稀土元素地球化学研究,分析结果表明:海相碳酸盐岩烃源岩稀土总量(∑REE)最大值75.21μg/g,最小值20.58μg/g,平均值为36.67μg/g.稀土元素北美页岩标准化后具有相对富集轻稀土,亏损重稀土的特点.布曲组碳酸盐岩烃源岩Ce/Ce*值为0.83～0.9...     

Mineralogy and geochemistry of clay fractions from different saprolites,Egypt: implications for the source of sedimentary kaolin deposits

The clay fractions of saprolites from granites, basalt, and schists in Egypt were subjected to mineralogical and geochemical investigations to examine the effect of source rock on the composition of the saprolites and the possibilities of these saprolites as a source of the nearby sedimentary kaolin deposits. The clay fractions of the studied saprolites show mineralogical and geochemical variations. Saprolites from the granites consist of kaolinite, while saprolites from the basalts are composed entirely of smectite. Schists-derived saprolites are composed of kaolinite in some cases and of a mixture of kaolinite, illite, and chlorite in the other. Saprolite from the basalt is characterized by relatively higher contents of TiO₂ and Ni compared to the saprolites from granites. Saprolites from granites have higher contents of Ba, Li, Pb, Sr, Th, Y, and Zr compared to those of the saprolites from the basalts and schists. Saprolites from different schists show variations in the distributions of many constituents, such as TiO₂, Cr, Ni, Ba, Y, and Zr. Although chondrite-normalized rare earth elements (REE) patterns are characterized by relative enrichments in the light rare earth elements (LREE) compared to the heavy rare earth elements (HREE) in all saprolites, granitic saprolites show negative Eu anomalies, while saprolite from basalt has no Eu anomaly. REE patterns of the saprolites from schists exhibit slight positive Ce anomalies and slight to moderate negative Eu anomalies. Weathering of saprolites from the basalt and metasediments is classified as the bisiallitization type, while weathering of saprolite from the granite is allitization type. Saprolites from schists vary from the bisiallitization (Aswan and Abu Natash) and allitization (Khaboba) types. Saprolites from the Khaboba schist can be considered the possible source of the Carboniferous kaolin deposits in the Hasber and Khaboba areas of Sinai, based on the similarity in the mineralogy and geochemistry of major, trace, and REE between the saprolites and the deposits. On the other hand, Carboniferous sedimentary kaolin deposits in the Abu Natash area, as well as the Cretaceous kaolin deposits in all areas of Sinai, might have been derived from the nearby schist saprolites, based on the similarity in the mineralogy and geochemistry between the saprolites and the kaolin deposits. Granites from the Arabian-Nubian Shield (ANS) and East Sahara Craton (ESC) are the possible sources of the pisolitic and plastic kaolin deposits in the Kalabsha area (Aswan), as indicated by the similarity in the mineralogy and geochemistry of the granitic saprolites and the kaolin deposits.     

Constraints on the Trace Element Composition of the Archean Mantle Root beneath Somerset Island, Arctic Canada

Peridotites that sample Archean mantle roots are frequentlyincompatible trace element enriched despite their refractorymajor element compositions. To constrain the trace element budgetof the lithosphere beneath the Canadian craton, trace elementand rare earth element (REE) abundances were determined fora suite of garnet peridotites and garnet pyroxenites from theNikos kimberlite pipe on Somerset Island, Canadian Arctic, theirconstituent garnet and clinopyroxene, and the host kimberlite.These refractory mantle xenoliths are depleted in fusible majorelements, but enriched in incompatible trace elements, suchas large ion lithophile elements (LILE), Th, U and light rareearth elements (LREE). Mass balance calculations based on modalabundances of clinopyroxene and garnet and their respectiveREE contents yield discrepancies between calculated and analyzedREE contents for the Nikos bulk rocks that amount to LREE deficienciesof 70–99%, suggesting the presence of small amounts ofinterstitial kimberlite liquid (0·4–2 wt %) toaccount for the excess LREE abundances. These results indicatethat the peridotites had in fact depleted or flat LREE patternsbefore contamination by their host kimberlite. LREE and Sr enrichmentin clinopyroxene and low Zr and Sr abundances in garnet in low-temperatureperidotites (800–1100°C) compared with high-temperatureperidotites (1200–1400°C) suggest that the shallowlithosphere is geochemically distinct from the deep lithospherebeneath the northern margin of the Canadian craton. The Somersetmantle root appears to be characterized by a depth zonationthat may date from the time of its stabilization in the Archean. KEY WORDS: Canada; mantle; metasomatism; peridotite; trace elements     

渝东南地区石牛栏组稀土元素地球化学特征及地质意义

渝东南地区的下志留统石牛栏组作为重要的油气储集层,研究其古环境变化、物质来源及物源区构造背景具有重要意义。本文采用稀土元素总量w(ΣREE)、REE配分模式、以及w(ΣLREE)/w(ΣHREE)、w(La)_N/w(Yb)_N、w(Ce)_N/w(Yb)_N、w(La)_N/w(Sm)_N、w(Gd)_N/w(Yb)_N、δEu、δCe、Ce_(anom)等特征值研究方法,对渝东南下志留统石牛栏组典型剖面的稀土元素特征及古海洋环境和物源进行深入研究。结果表明:石牛栏组灰岩稀土元素总量略低于大陆地壳平均值,轻稀土较为富集,重稀土亏损,铕明显负异常,铈负异常较微弱。w(ΣREE)证实了石牛栏组的沉积水体由浅缓慢变深再急剧变浅的变化过程。Eu负异常、Ce负异常和C_(eanom)值均揭示石牛栏组沉积时期海水具有弱还原性。REE的分异程度反映了石牛栏组从沉积早期到沉积晚期,沉积速率总体降低。稀土元素的比值特征及w(ΣREE)—w(La)/w(Yb)图解表明其物源源自雪峰山隆起,源岩主要为沉积岩。