Rare earth element distributions in some Precambrian rocks and their phyllosilicates,Numedal, Norway

Mass spectrometric analyses for rare earth elements (REE) have been carried out on some Precambrian mica schists, gneisses and granites from the Precambrian Numedal area, Norway and on their phyllosilicates. The rocks, which are metamorphosed in the upper greenschist to amphibolite facies, were originally partly sedimentary, partly magmatic.The total REE contents for rocks varies from 145 to 761 ppm. An average of 16 phyllosilicate samples gave 417 ppm REE (max. of 1809 ppm, min. of ca. 50 ppm). Coexisting light and dark phyllosilicates have similar abundances of REE. For the micas of high REE content most of the REE was extractable by rinsing with EDTA. The data thus support the possibility of an extensive adsorption of REE ions on micaceous minerals. The REE distribution patterns do not provide a clear distinction between the sedimentary and magmatic origin for the rocks examined.     

Rare earth elements in some igneous rocks in the Oslo rift, Norway

Rare earth element (REE) concentrations have been determined for 27 plutonic rocks in the Permian Oslo rift, including kjelsåsite/larvikites, lardalites, nordmarkites, ekerites and Drammen granites.

The kjelsåsite/larvikites from different parts of the rift have very similar REE concentrations and must be derived from a source or sources homogeneous with respect to REE.

The genetic relations between the kjelsåsite/larvikites and the other rocks were tested by comparing observed REE enrichment factors with calculated ones based on hypothetical fractionation relations derived from petrographic mixing calculations. Several of the analyzed nordmarkites may be derived from kjelsåsitic/larvikitic parent magmas: the ekerites are closely related to the nordmarkites.     

Rare earth elements in tektites

Four moldavites and one sample each of an australite, billitonite, indochinite, philippinite, thailandite, Ivory Coast tektite, bediasite and a georgianite were analyzed using neutron activation analysis for La, Ce, Sm, Eu, Tb, Yb and Lu. The REE abundances resemble those of sedimentary rocks. Most of the tektites display a depletion of Eu, a characteristic feature of mature Phanerozoic continental sedimentary rocks. However, the Ivory Coast tektite and georgianite are relatively enriched in Eu, possibly due to the presence of plagioclase-rich source rocks.     

Rare earth elements as tracers of sediment contamination by phosphogypsum in the Santos estuary,southern Brazil

In the Cubatão region, southern Brazil, sediments are transported by several rivers from the Serra do Mar Ridge into the Santos estuary. Fertilizer plants have been operating along the margins of one of these rivers (Mogi River) producing a large volume of phosphogypsum, which is stockpiled in nearby areas. Surface sediments of the Mogi River were sampled upstream and downstream in relation to the point where the effluents of the phosphogypsum piles flow into the drainage system. In the vicinity of this point one sediment core was collected. Results show that REE, Ba, Zr and Th concentrations in the non-contaminated sediments are of the same order as those present in the upper continental crust. The contaminated samples present a composition affected by that of the phosphogypsum, marked by a higher concentration of these elements and a stronger degree of REE fractionation. These phosphogypsum characteristics are inherited from the Catalão igneous phosphate ore and were moderately modified by the industrial process of phosphoric acid production. The phosphogypsum signal decreases rapidly downstream, pointing to a limited area of influence of the stacks. The deepest sediments of the core are also free of contamination, representing a time interval prior to the deposition of phosphogypsum wastes on the banks of the estuary.     

Rare earth element geochemistry of the Fen alkaline complex,Norway

Determination of rare earth element (REE) abundances in rocks of the Fen complex has shown that within rocks of the first magmatic series REE abundances increase in the order urtiteFen magmas are discussed and it is considered that parental magmas had relatively high La/Yb ratios (40–60). Utilizing petrological evidence from other alkaline complexes coupled with experimental studies it is considered that the parental magma was a carbonated nephelinite produced by limited (<10%) partial melting of the mantle. All the Fen rocks are placed in a petrogentic scheme in which a carbonated nephelinite magma undergoes liquid immiscibility, differentiation and volatile transport.     

Rare earth elements in granitic rocks

The younger granites in Finland contain more REE than the older ones. In the youngest, postorogenic rapakivi granites, the total REE concentration is highest, the light REE are more enriched, and the negative Eu anomaly is more pronounced than in the older granites. The enrichment of the light REE, the anomalous behavior of the extreme elements (La, Ce, and Lu) in normalized graphs, and the depletion of Eu indicate the degree of differentiation the rock has undergone. These features are usually more pronounced in large, homogeneous granites than in metamorphic or volcanogenic rocks. Silicic vein rocks usually contain less REE than the granites proper; the distribution pattern in many is as in granites, but in some the heavy elements are more enriched. The positive Eu anomaly in Precambrian metamorphic rocks is tentatively attributed to metamorphic differentiation and to the secretion of silicic material from the host rock.     

Rare earth elements in supergene phosphorites

An analysis of rare earth elements in various types of supergene phosphorites established the following sequence of increasing average total contents (ppm): phosphorite from Christmas Island in the Indian Ocean, 3.89; spelean coprolitic phosphorite, 21.98; phosphorite from the weathering zone of sedimentary rocks, 27.41; phosphorite from the weathering zone of endogenous rocks, 372.32; and lacustrine coprolitic phosphorite, 461.59. Supergene phosphorites, especially the most common among them from the weathering zone of sedimentary rocks, are significantly depleted relative to marine phosphorites both in average and maximum REE contents. The REE contents of supergene phosphorites are controlled by several factors, including the REE contents in the primary rocks affected by weathering, the physicochemical conditions of phosphorite formation, the presence of a biogenic component in the phosphatogenetic system, and the structural type of the phosphorites. There is a strong positive correlation within the group of light and, in part, middle REEs (La, Ce, Nd, Sm, and Eu) and between the heavy REEs Yb and Lu, whereas the correlation between these two groups is weaker or insignificant. Gd and Tb are well correlated with the elements of both groups.     

Rare earth elements in alpine peridotites

The samples from alpine peridotite massifs (Beni Bouchera, Lherz and the Alps) have been analyzed for rare earth elements. The peridotites as a whole are characterized by various degrees of light REE depletion (Ce varies from 1.2 to 0.02 times chondrite) and a small variation in heavy REE (Yb varies about a factor of 2, from 1.3 to 2.2 times chondrite). They show a restricted and regular distribution in a Ce-Yb diagram, giving two types of linear trends for individual massifs (trend A for the Alps and Lizard; trend B for Beni Bouchera and Lherz, branching from trend A). The model calculations of partial melting based on the partition relations of REE among silicate minerals and melts suggest that trend A could represent a series of residua left after partial melting of garnet peridotite despite the fact that there is no garnet observed in the peridotites studied here. It is suggested that trend A would represent a melting event which predated the emplacement of the massifs and occurred at higher pressure (in the presence of garnet) than expected from the present mineralogy. The calculations also suggest that trend B could represent a partial melting event at lower pressures than trend A after the massifs uplifted into spinel peridotite field. It is also suggested that the REE concentrations of the mantle could be estimated as 2–2.5 times chondrite.     

Rare Earth Elements in Egyptian Phosphorites

Egyptian phosphorites from Abu Tartur(Western Desert),El Mahamide mine(Nile Valley) and Rabah mne(Eastern Desert)show variable degrees of relative REE enrichment.Black plateau phosphorites of Abu Tartur are substantially enriched in REE as compared to the Red Sea and Nile Valley phosphorites.P-rich organic matter from the Abu Tartur and Rabah mines recorded negative Ce and positive Eu anomalies.Positive Eu anomaly reveals an anoxic event prior to the phase of Late Cretaceous phosphate formation.Ce is a redox indicator.Mixing of sea water and upwelling during the Late Cretaceous was responsible for the recording of positive Eu and negative Ce anomalies in the Egyptian phosphorites.     

Rare earth elements,iron formations and sea water

Iron formations probably formed as chemical sediments when an Fe-rich solution entered the sedimentary environment. The REE patterns of such sediments are affected by the amount and type of precipitating and detrital phases, the REE pattern of the iron source solution, the REE pattern of the sea water into which the solution flows, and the mixing which takes place between input solution and sea water. What is known about the different types of iron formation suggests that all of these factors may vary from one type to another. Therefore, variations in REE patterns cannot be attributed solely to changes in sea water REE patterns. Comparison of the REE patterns of Archean and Ordovician iron formations of the Algoma type shows that similar iron formations have similar REE patterns regardless of age. This implies similar genetic histories.     

福建丁家山铅锌矿稀土元素特征

通过对福建丁家山矿区铅锌矿床不同类型岩石和矿石的稀土元素地球化学特征的研究,探讨了岩石和矿石中稀土元素地球化学行为。结果显示,丁家山铅锌矿区的稀土元素呈现轻稀土富集、重稀土亏损的地球化学特征,说明成矿流体和围岩具有继承性,丁家山铅锌矿虽呈层状,但该矿床具有热液矿床的特征。热液在运移过程中,随着温度不断降低,在成矿有利部位形成低温蚀变矿物,如绿泥石、绿帘石、阳起石等,同时伴随着Cu、Pb、Zn、Ag等成矿元素和稀土元素的沉淀富集。     

Rare earth elements in the early Archaean Isua iron-formation, West Greenland

The rare earth element (REE) patterns in the 3.8 Ga-old Isua iron-formation are generally flat, resembling those of some primitive basalts. Samples with positive, negative or no europium anomaly were found. It is shown that diagenesis and metamorphism did not significantly change the REE patterns. The presence or absence of europium anomalies in iron-formations cannot be used as an indicator of the presence or absence of oxygen in the atmosphere during the Archaean and Precambrian. The REE contents cannot be used to distinguish Algoma-type from Superior-type iron-formations. There appears to be a striking similarity between the Archaean submarine exhalations and modern submarine hydrothermal systems. It is considered likely that Archaean and early Precambrian seawater had a chondritic REE pattern with a slight enrichment of light REE.     

Rare earth elements in Permian salts and brines,Thuringia, Germany

Salts and brines have very low rare earth element (REE, La-Lu) concentrations. Thus, there is less knowledge of possible transfer of REE patterns during salt dissolution in water-rock interaction. REE levels in both media are close to or rather below limit of detection of commonly used methods. By dissolving salt samples in water followed by REE pre-concentration, REE contents of about 6.2 to 322 ng g⁻¹ were measured for four samples from the Merkers salt mine, Germany. These salts previously were identified to consist mainly of carnallite, halite and/or sylvite. Assuming congruent dissolution, REE patterns of brines and salts differ. Thus, a more complex interaction with (secondary) phases and complexation of REE should be taken into account to explain REE patterns in brines.     

Rare earth elements in ‘Younger’ granites,Northern Portugal

Rare earth elements (REE) were determined in two suites of Hercynian ‘Younger’ granodiorites and granites, one massive and the other porphyritic. Within each suite, the REE abundances decrease towards the more felsic granite while the REE patterns are almost identical. The patterns of the porphyritic types are only slightly more fractionated than those of the massive rocks. Negative Eu-anomalies are observed in all rocks although those of the granodiorites are smaller than those of the granites. Modeling of the data indicates that the granitic magmas may be derived, by partial melting, from the greywackes and pelites of the orogenic belt, the melts being in equilibrium with a residuum composed of quartz, plagioclase, garnet, orthopyroxene or cordierite, and, possibly, biotite.     

Rare earth elements in pore waters of marine sediments

The rare earth elements (REEs) were measured in pore waters of the upper ∼25 cm of sediment from one site off Peru and three sites on the California margin. The pore water REE concentrations are higher than sea water and show systematic down core variations in both concentration and normalized pattern. From these analyses and from comparison to other chemical species measured (dissolved Fe, Mn, Ba, oxygen, nitrate, phosphate), it is suggested that pore water REEs can be grouped into three categories: those that are from an Fe-source, those that are from a POC-source, and cerium oxide. REEs from the Fe-source appear where anoxia is reached; they have a distinctive “middle-REE (MREE) enriched” pattern. The concentrations in this source are so elevated that they dominate REE trends in the Fe-oxide reduction zone. The net result of flux from the POC-source is relative enrichment of heavy-REEs (HREEs) over light-REEs (LREEs), reflecting remineralizing POC and complexation with DOC. A common “linear” REE pattern, seen in both oxic and anoxic sediments, is associated with this POC-source, as well as a “HREE enriched” pattern that is seen in surficial sediments at the Peru site. Overall, the pore water results indicate that Mn-oxides are not an important carrier of REEs in the oceans.A REE biogeochemical model is presented which attempts to reconcile REE behavior in the water and sediment columns of the oceans. The model proposes that POC, Fe-oxide and Ce-oxide sources can explain the REE concentration profiles and relative abundance patterns in environments ranging from oxic sea water to anoxic pore water. The model is also consistent with our observation that the “Ce-anomaly” of pore water does not exceed unity under any redox condition.     

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 elements in a sampled coal from the Pirin deposit,Bulgaria

Rare earth elements (La, Ce, Sm, Eu, Tb, Yb, and Lu) in a columnar section of the coal of the Pirin deposit, Bulgaria, have been determined by neutron activation analyses.The REE content in the coals is lower than the average REE content of shales from North America, Europe, and the Soviet Union. The REE abundances increase with the increasing ash content of the coals. The bottom of the seam is slightly enriched in REE, the trend being more pronounced in HREE (Tb, Yb, Lu). The REE content depends on the thickness of the coal layers: the thin coal layers are enriched in REE as compared to the thick ones.The chondrite-normalized distribution patterns are very uniform. They are characterized by a negative Eu anomaly whose mean value is 0.30 (varying in the individual samples from 0.21 to 0.49) and a positive Lu anomaly. It is supposed that the Eu anomaly is inherited from the source rocks.The shale-normalized distribution patterns show a distinct relative enrichment in HREE and a negative Eu anomaly. The relative enrichment in HREE is a specific feature of the REE geochemistry in the Pirin deposit. The LREE/HREE ratio is lower than that of composite shale; it increases with the increasing ash content of the coals and from the bottom to the top of the coal bed.REE are bound predominantly to the aluminosilicates of the mineral matter in the coals. All REE are positively correlated to the ash, Si, Al, Fe, and Na.The source of REE in coals is mainly the suspended terrigenous material. The specific enrichment of REE in the ash of low-ash coals is a result of the interaction between the dissolved REE and the products of disintegration and decay of organic substances, mainly the humic acids.     

Rare earth elements in the peats of Moscow and Tver oblasts

Noticeable amounts of rare-earth elements were first detected in the peats of the earlier drained bogs of Moscow and Tver oblasts. The analysis was carried out by inductively coupled plasma mass spectrometry on an ELAN DRC II instrument (PerkinElmer, United States). The contents of REEs in peat ash of certain deposits are higher than their average contents in the basic rocks and vary in the range of 0.5–60 and 0.1–41.3 mg/kg for the cerium and yttrium groups, respectively.