Middle Rare Earth Element Enrichment Research Articles

Chemical effect of pesticide application on soils: evidence from rare earth elements

The main objective of this study is to investigate the distribution of rare earth elements (REEs) in Lolium perenne L. plant species which has been grown on vineyard soils treated with pesticide commonly used in the study area. These plants have been grown on two types of soils: (1) brown calcareous soils developed on loess and (2) brown to calcic brown soils developed on conglomerates. The significant correlation observed between the concentrations of phosphorus and the total amount of REEs, in addition to the enrichment in middle REEs (MREEs), suggests the complexation of REEs with phosphates and organic matter. The soils were enriched in REEs due to pesticide application but the plants were depleted. The ratio of REEs in plant over REEs in soil before application of pesticides is higher than that after application of pesticides. Application of pesticides to crops did not affect the fractionation of REEs neither in leaves nor in roots. No selectivity in uptake of REEs occurred because of pesticides except for Ce and Eu which show a negative anomaly relative to the other REEs.

Geochemical characteristics of shales in the Mamfe Basin, South West Cameroon: Implication for depositional environments and oxidation conditions

Field and laboratory studies were carried out with the aim of characterizing the depositional environment and oxidation conditions during accumulation of shales in the Mamfe basin. Field studies denoted that the shales were black to dark grey in color, sub-tabular to tabular in occurrence, with some (n = 20) reacting vigorously with dilute HCl, while others did not (n = 5). Due to the carbonate content of the samples both whole rock dissolution and partial dissolution, using dilute acetic acid to target the carbonate fraction in the samples, were employed. The seven shale-rich units investigated have average whole rock Ni/Co, V/Cr, U/Th and Th/U ratios of 1.68–2.0, 1.13–2.95, 0.24–0.51 and > 2, respectively. PAAS normalized rare earth elements in the whole rock samples display an enrichment of light rare earth elements (LREEs) over heavy rare earth elements (HREEs), middle rare earth elements (MREEs) over HREEs, positive Gd, Eu anomalies, no Ce anomalies, and an average Y/Ho ratio of 29.7 ppm. The carbonate fraction of the samples displays two different REE pattern types. Sites 1 and 6 have typical hat-shaped patterns with extensive MREE enrichment. The other locations are slightly HREE depleted and have weak MREE enrichment with negative Y anomalies. The trace element ratios and the REE patterns of the whole rock and carbonate fractions indicate that the sediments deposited in the Mamfe basin accumulated in non-marine environments. Furthermore, their coloration, MREE enrichment and lack of Ce anomalies in the carbonate fractions infers that the depositional area was in a vegetated, low-land lacustrine setting with limited oxygenation of the sediment, whereas the negative Ce anomalies in the whole rock shale samples is probably due to particulate scavenging of REEs from the fluid during transport. This would require the water to be deficient in Ce and, thus reflect oxidizing conditions in the source area and along the transport system.

Yttrium and rare earth elements fractionation in salt marsh halophyte plants

Salt marshes act as natural deposits of different metals (e.g. heavy-metals), while halophyte plants are known to retain and accumulate them in the different tissues. Scarce data exists on accumulation, partition and fractionation of YREE in these plants. To study the relationship between halophyte plants and YREE, contents of these metals were determined by ICP-MS in sediment, and in the different plants organs, from Rosário's salt marsh, in Tagus estuary (SW Europe). Results show significant differences (p < 0.001) in YREE contents between sediments. In non-colonised sediment Y was lower (5.0–18 mg·kg−1) compared to the Sarcocornia fruticosa and Spartina maritima sediment cores (19–26 and 20–26 mg·kg−1, respectively). The same was observed for ΣREE, with lower values in non-colonised sediment (32–138 mg·kg−1), while colonised ones presented higher contents (146–174 and 151–190 mg·kg−1, for S. fruticosa and S. maritima, respectively). These significant differences (p < 0.05) are explained by the sediments' nature. Yttrium and ΣREE Al-normalised ratios in non-colonised sediment ranged from 1.5 to 2.3 and 11 to 13, respectively. The colonised sediments revealed significant higher ratios (particularly for ΣREE/Al ratios; p < 0.001), varying from Y/Al: 1.8–2.3 and ΣREE: 13–16 for S. fruticosa, and Y/Al: 1.4–2.3 and ΣREE: 12–18, for S. maritima. Results suggest that these plants may promote YREE enrichment in the sediments. No differences in fractionation patterns among sediments and in both species roots were found, but fractionation was different from those in the sediment, with similar middle-REE (MREE) enrichment and no light-REE (LREE) and heavy-REE (HREE) fractionation. No evidence of YREE transfer to aboveground organs was observed. Different fractionation patterns in stems and leaves were registered, with clear enrichment of LREE relative to HREE and an increase in the MREE enrichment. Therefore, these plants showed low ability to accumulate and translocate YREE but may promote its enrichment in the sediments.

Glauconite-bearing sedimentary phosphorites from the Tébessa region (eastern Algeria): Evidence of REE enrichment and geochemical constraints on their origin

Rare earth element (REE) analyses are reported on glauconite-bearing phosphorites from northeastern Algeria. These rocks of Paleocene-Eocene age are located in the Eastern part of the Saharan Atlas, where two localities were investigated: the Djebel El Kouif in the north and the Kef Essenoun in the south. The latter belongs to the world-class Djebel Onk mining deposit. Petrographic examination indicates that phosphorite from the main layer of the Kef Essenoun deposit has a significant abundance in glauconite grains, while their occurrence in the Djebel El Kouif is restricted to the basal levels. In both deposits, glauconite grains are richer in REEs than other co-existing particles (pellets, coprolites, enameloid and dentine of marine fish teeth), but the glauconites of the Kef Essenoun deposit exhibit significantly higher REE concentration (min = 654 ppm, max = 1760 ppm, average = 1146 ppm) than those of Djebel El Kouif deposit (min = 543 ppm, max = 623 ppm, average = 584 ppm). The whole-rock REE concentrations also show substantial differences between the two deposits and the REE enrichment in the Kef Essenoun main sub-layer is more likely the result of the high glauconite content. PAAS normalized-REE patterns of the glauconite grains display similar patterns between the northern and southern localities with weak negative Ce anomalies and slight middle REE enrichments. On the other hand, the pellets and whole phosphorite grains from the northern deposit indicate a REE source from oxic-suboxic seawater, whereas those from the Kef Essenoun deposit exhibit slight middle REE enriched patterns with weak negative Ce anomaly suggesting a different environment of deposition (i.e. a tendency to reduced conditions). These geochemical results along with previous petrographic studies confirm the allochthonous character of the main phosphorite sub-layer in Kef Essenoun, where winnowing, transport and re-deposition of previously deposited phosphorites resulted in high accumulation and formation of glauconite grains. The glauconitization process of fecal pellets happened in two stages and was controlled by semi-confined micro-environments. This can explain the abundance of glauconite grains in the phosphorites from Kef Essenoun deposit and their restricted occurrence in the basal levels of the Djebel El Kouif outcrop.

Element distribution in fruiting bodies of Lactarius pubescens with focus on rare earth elements

During growth and senescence, fungal fruiting bodies accumulate essential and non–essential elements to different extent in their compartments. This study bases on a dataset of 32 basidiocarps of the ectomycorrhizal Lactarius pubescens sampled in a former U mining area. Statistical analyses were combined with rare earth element (REE, La–Lu) patterns to study the element distribution within sporocarp compartments and between three different age classes. For this purpose, fruiting bodies were separated into stipe, pileus trama, pileipelles and lamellae, dried and digested with HNO3.While macronutrient (e.g. K, Mg, P, S) contents resemble those of a non–mining affected site, several elements (e.g. Co, Mn) were site–specifically taken up relative to elevated soil contents. With statistics, two main element distribution groups for L. pubescens were revealed: mainly essential (Cu, Mg, Mn, P, S, Zn, Cd, Co, Ni) and mainly non–essential elements (Al, Ca, Fe, Sr, U, REE). The highest REE contents were found in pileipelles and lamellae, corresponding to relatively small cell sizes. Stipes and pileus trama had low REE contents due to their function as transport systems. During growth, light REE (La–Nd) were strongly enriched in lamellae and pileipelles. Middle REE (Sm–Dy) enrichment was found both in soil and fungal biomass.Contents of nutrients decrease with age, while non–essential elements are enriched especially in pileipelles and lamellae. A weak positive Ce anomaly appeared in the bioavailable soil fraction and in the pileipelles of younger individuals. Substrate dependent uptake thus gets reduced with sporocarp senescence, possibly due to redistribution.

Mineralogical controls on mobility of rare earth elements in acid mine drainage environments

Rare earth elements (REE) were analyzed in river waters, acid mine waters, and extracts of secondary precipitates collected in the Iberian Pyrite Belt. The obtained concentrations of the REE in river water and mine waters (acid mine drainage - AMD) were in the range of 0.57 μg/L (Lu) and 2579 μg/L (Ce), which is higher than previously reported in surface waters from the Iberian Pyrite Belt, but are comparable with previous findings from AMD worldwide. Total REE concentrations in river waters were ranged between 297 μg/L (Cobica River) and 7032 μg/L (Trimpancho River) with an average of 2468 μg/L. NASC (North American Shale Composite) normalized REE patterns for river and acid mine waters show clear convex curvatures in middle−REE (MREE) with respect to light- and heavy−REE.During the dissolution experiments of AMD-precipitates, heavy−REE and middle−REE generate the most enriched patterns in the solution. A small number of precipitates did not display MREE enrichment (an index Gdn/Lun < 1.0) in NASC normalized pattern and produced relatively lower REE concentrations in extracts. Additionally, very few samples, which mainly contained aluminum sulfates, e.g., pickeringite and alunogen, displayed light−REE enrichment relative to heavy−REE (HREE). In general, the highest retention of REE occurs in samples enriched in magnesium (epsomite or hexahydrite) and aluminum sulfates, mainly pickeringite.

The Influence of Basaltic Islands on the Oceanic REE Distribution: A Case Study From the Tropical South Pacific

The Rare Earth Elements (REEs) have been widely used to investigate marine biogeochemical processes as well as the sources and mixing of water masses. However, there are still important uncertainties about the global aqueous REE cycle with respect to the contributions of highly reactive basaltic minerals originating from volcanic islands and the role of Submarine Groundwater Discharge (SGD). Here we present dissolved REE concentrations obtained from waters at the island-ocean interface (including SGD, river, lagoon and coastal waters) from the island of Tahiti and from three detailed open ocean profiles on the Manihiki Plateau (including neodymium (Nd) isotope compositions), which are located in ocean currents downstream of Tahiti. Tahitian fresh waters have highly variable REE concentrations that likely result from variable water–rock interaction and removal by secondary minerals. In contrast to studies on other islands, the SGD samples do not exhibit elevated REE concentrations but have distinctive REE distributions and Y/Ho ratios. The basaltic Tahitian rocks impart a REE pattern to the waters characterized by a middle REE enrichment, with a peak at europium similar to groundwaters and coastal waters of other volcanic islands in the Pacific. However, the basaltic island REE characteristics (with the exception of elevated Y/Ho ratios) are lost during transport to the Manihiki Plateau within surface waters that also exhibit highly radiogenic Nd isotope signatures. Our new data demonstrate that REE concentrations are enriched in Tahitian coastal water, but without multidimensional sampling, basaltic island Nd flux estimates range over orders of magnitude from relatively small to globally significant. Antarctic Intermediate Water (AAIW) loses its characteristic Nd isotopic signature (-6 to-9) around the Manihiki Plateau as a consequence of mixing with South Equatorial Pacific Intermediate Water (SEqPIW), which shows more positive values (-1 to -2). However, an additional Nd input/exchange along the pathway of AAIW, eventually originating from the volcanic Society, Tuamotu and Tubuai Islands (including Tahiti), is indicated by an offset from the mixing array of AAIW and SEqPIW to more radiogenic Nd isotope compositions.

Mineralogical and Geochemical Discrimination of the Occurrence and Genesis of Palygorskite in Eocene Sediments on the Northeastern Tibetan Plateau

AbstractPalygorskite is a widely used indicator of semiarid to arid environments in paleoclimate studies. In this study, we present detailed mineralogical and geochemical investigations exploring the genesis of palygorskite found in Eocene fluvial sediment in the northern Qaidam Basin on the northeastern Tibetan Plateau. The presence of two types of palygorskite is revealed, based on their crystallinity characteristics and distinctive rare earth element (REE) patterns in the coexisting clay fraction. Well‐crystallized palygorskite samples are characterized by remarkably negative Ce anomalies and obvious middle rare earth element enrichment. Poorly crystallized palygorskite samples generally exhibit positive Ce anomalies and less pronounced middle rare earth element enrichment, which resemble those of nonpalygorskite‐bearing clay samples. Given the presence of an overall oxidized fluvial sedimentary environment, we attribute the well‐crystallized palygorskite (which has textures comprising long, interwoven fibers) to direct precipitation (i.e., neoformation) occurring within a reducing environment during early/postdepositional processes while the poorly crystallized palygorskite (which is characterized by short, club‐shaped single crystals) originates as catchment‐delivered detritus. These poorly crystallized palygorskites occur mostly in 49.5–47.0 Ma and are accompanied by decreasing kaolinite content, increasing chlorite content, and abundant xerophytic spore‐pollen from the Qaidam Basin, and its neighboring Xining Basin. Collectively, these evidences suggest that a less humid climate followed after the Early Eocene Climate Optimum.

Environmental geochemistry of near-neutral waters and mineralogy of zinc and lead at the Angouran non-sulphide zinc mine, NW Iran

This study aims to investigate the geochemistry of major ions, trace and rare earth elements (REE) near the Angouran Zn-Pb mine. Thermodynamic modelling and saturation indices were computed using PHREEQC. Process and tailings water samples of the Calcimin processing plant were near neutral (pH=5.8–7.9) and had high concentrations of SO4 (1179–15,000mg/L), Zn up to 18,529mg/L, Pb up to 1780μg/L, As up to 465μg/L and Cd up to 230μg/L. Water of the Angouran pit was neutral-alkaline (pH=7.6–8.25) with low concentrations of SO4 (21–87mg/L), elevated concentration of Zn up to 27mg/L, Pb up to 586.3μg/L and Cd up to 33μg/L. Water flowing out of the Angouran Mine adit was neutral-alkaline (pH=7.5–8.05) with variable SO4 content (30–2294mg/L), Zn content up to 8mg/L, Pb up to 123μg/L and As up to 35.4μg/L. Elements As, Pb, Cd, Ni and Zn concentrations in the plant waters were higher than USEPA effluents limits. Generally, the types of water in the plant and the mine ranged from Zn-SO4, Na+K-SO4 to Ca-HCO3, respectively. North-American Shale Composite (NASC) normalised patterns of the mine and the spring water samples showed middle REE (MREE) and high REE (HREE) enrichment. The most toxic elements including Pb, Cd, Ni, and Zn were predicted as cationic form in the plant water. The prediction further showed that smithsonite (ZnCO3), hydrozincite Zn5(OH)6(CO3)2, hemimorphite Zn4Si2O7(OH)2, and beudantite (PbFe3(AsO4)(SO4)(OH)6) were oversaturated in some water samples.

Rare earth element geochemistry characteristics of seawater and porewater from deep sea in western Pacific

Deep-sea sediments contain high concentrations of rare earth element (REE) which have been regarded as a huge potential resource. Understanding the marine REE cycle is important to reveal the mechanism of REE enrichment. In order to determine the geochemistry characteristics and migration processes of REE, seawater, porewater and sediment samples were systematically collected from the western Pacific for REE analysis. The results show a relatively flat REE pattern and the HREE (Heavy REE) enrichment in surface and deep seawater respectively. The HREE enrichment distribution patterns, low concentrations of Mn and Fe and negative Ce anomaly occur in the porewater, and high Mn/Al ratios and low U concentrations were observed in sediment, indicating oxic condition. LREE (Light REE) and MREE (Middle REE) enrichment in upper layer and depletion of MREE in deeper layer were shown in porewater profile. This study suggests that porewater flux in the western Pacific basin is a minor source of REEs to seawater, and abundant REEs are enriched in sediments, which is mainly caused by the extensive oxic condition, low sedimentation rate and strong adsorption capacity of sediments. Hence, the removal of REEs of porewater may result in widespread REE-rich sediments in the western Pacific basin.

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt, Xinjiang (NW China)

The Neoproterozoic (593–532Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al2O3 and TiO2, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al2O3 (<3wt%), TiO2 (<0.15wt%), ∑REE (5.06–39.6ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al2O3 (>3wt%), TiO2, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu∗PAAS=2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu∗PAAS=1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe3+/(Fe3+/Fe2+) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ13CV-PDB (−4.0‰ to −6.6‰) and δ18OV-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ13CV-PDB=−0.8‰ to +3.1‰ and δ18OV-PDB=−8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu∗PAAS and δ13CV-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO2, with the deeper water, from which the carbonate facies BIF formed, depleted in δ13C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe2+-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe2+-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.

Comparison between Datangpo-type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on rare earth elements

Datangpo-type sedimentary manganese deposits, which are located in northeastern Guizhou province and its adjacent areas, are Mn carbonate-type deposits hosted in black carbonaceous shale that represent a series of medium to large deposits containing a huge tonnage of reserves. PAAS-normalized rare earth element distribution patterns of manganese ores record “hat-shaped” REY (REE+Y) plots characterized by pronounced middle rare earth element enrichment, evident positive Ce anomalies, weak to strong positive Eu anomalies and negligible negative Y anomalies. These REY geochemical characteristics are different from those of country rocks and record the processes and features of sedimentation and diagenesis. Manganese was precipitated as Mn-oxyhydroxide particles in oxidized water columns with the sorption of a certain amount of rare earth elements, subsequently transforming from Mn-oxyhydroxides to rhodochrosite and redistributing REY in reducing alkaline pore-water during early diagenesis. A number of similarities can be observed through a comparison of Datangpo-type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on their rare earth elements. The precipitation of Datangpo-type manganese ores is similar to that of hydrogenetic crusts and nodules based on their positive Ce anomalies and relatively higher total REY concentrations. However, several differences also exist. Compared to hydrogenetic crusts and nodules, Datangpo-type manganese ores record smaller positive Ce anomalies, lower total REY concentrations, unobvious fractionation between Y and Ho, and weak to strong positive Eu anomalies. These were caused by quicker sedimentary rates in the oxic water columns of the shallower basin, after which pore water became strongly reducing and alkaline due to the degradation of organic matter in the early diagenetic stage. In addition, compared to typical deposits in the world, Datangpo-type manganese ores are similar to hydrogenetic deposits and different than hydrothermal deposits. All of these characteristics of manganese ores indicate that Datangpo-type manganese ores, the principal metallogenic factors of which include oxidation conditions during deposition and reducing conditions during early diagenetic stages, represent hydrogenetic deposits.

A LA-ICP-MS analysis of rare earth elements on phosphatic grains of the Ediacaran Doushantuo phosphorite at Weng'an, South China: implication for depositional conditions and diagenetic processes

AbstractThe Ediacaran Doushantuo Formation at Weng'an, South China hosts well-preserved phosphatized microfossils known as the Weng'an biota. A laser ablation ICP-MS analysis of rare earth element (REE) characteristics of the fossil-bearing black phosphorite unit of the Doushantuo Formation at Weng'an was conducted, with the aim of unravelling the depositional conditions and diagenetic processes during formation of the phosphorites. Spherical phosphatized microfossils and phosphatic clasts were analysed, and the REE data display middle REE (MREE) -enriched shale-normalized REE patterns. The spherical phosphatized microfossils show an increase in total REE contents (∑REE) from core to rim. Negative correlations between ∑REE and the extent of MREE enrichment over the other REE (indicated by LaN/SmN, YbN/SmN) are observed for analysed spots within individual phosphatic grains, which may be due to complex diagenetic history of the phosphatic grains, with fluctuations in REE sources and chemical parameters in a high-energy shallow-water environment being additional factors. The LaN/YbNand LaN/SmNcharacteristics of the phosphatic grains suggest they were mostly influenced by early diagenetic alteration rather than late extensive recrystallization. The negative Ce anomalies in the samples suggest they formed under oxic-bottom-water conditions. Positive Eu anomalies are present in all samples, and are likely to reflect involvement of hydrothermal fluids rather than changes in redox conditions of porewater. Overall this study has major implications for phosphorites as important archives for the study of geochemical proxies, the Ediacaran period and also evolutionary changes.

Distribution and fractionation of rare earth elements and Yttrium in suspended and bottom sediments of the Kali estuary, western India

Concentrations of rare earth elements (REE) and yttrium (Y), and major metals (Al, Fe and Mn) were measured in suspended particulate matter (SPM) and bottom sediments of the Kali estuary, western India, for their distribution and fractionation. The contents of SPM and metals in it were more uniform along the longitudinal transect during the monsoon. During the post- and pre-monsoons, low SPM in the upper/middle estuary coincided with high Fe and Mn and total REE (∑REE). But in the lower estuary SPM and its ∑REE content increased seaward, while Fe and Mn decreased. The Y/Ho ratios decreased seaward during the monsoon but increased during the post-monsoon. Sm/Nd ratios were more uniform along the transect during monsoon but decreased marginally seaward in other seasons. The Post-Archean Average Australian Shale (PAAS)-normalized REE patterns exhibited middle REE and heavy REE enrichment with positive Ce ($${\text{Ce}}/{\text{Ce}}^{*}$$ ), Eu ($${\text{Eu}}/{\text{Eu}}^{*}$$ ) and Y anomalies. The $${\text{Ce}}/{\text{Ce}}^{*}$$ increased but $${\text{Eu}}/{\text{Eu}}^{*}$$ decreased marginally seaward. The fine-grained sediments showed higher ∑REE and lower Y/Ho ratios than in coarse-grained sediments. The PAAS-normalized REE patterns of sediment were similar to that of SPM. The results revealed two processes, colloidal flocculation and coagulation of metals in the low-salinity zone and an estuarine turbidity maximum in the high salinity zone. Rare earths and yttrium (REY) in SPM and sediments primarily reflected the source rock composition than that of chemical weathering. Apart from physico-chemical processes, the mineralogy and grain size of sediments controlled the distribution and fractionation of REY in the estuary.

Acidic drainage drives anomalous rare earth element signatures in intertidal mangrove sediments

Sedimentary rare earth element (REE) signatures can provide powerful insights into nearshore biogeochemical processes and anthropogenic influences. Despite this, there is limited research investigating REE behaviour in sediments influenced by coastal acid sulfate soils (CASS). Here, we explore REE abundance and fractionation in intertidal mangrove sediments that received CASS drainage for ~15–20y within the Hastings Catchment in NSW, Australia. Sediments close to the CASS discharge point (<200m) were compared with those further downstream (1300–1600m), and at a nearby control site. Average ΣREE concentrations were highest near the CASS discharge point (148–186mg/kg), and decreased with distance downstream (111–146mg/kg) and in control sediments (70mg/kg). Reactive Fe concentrations (defined by 1M HCl extractability) were also significantly higher in surface sediments (0–6cm) near the CASS discharge point. Middle-REE (MREE) enrichments dominated fractionation patterns at all sites (>1.5), with a high proportion (63–100%) of REEs residing in the reactive (1M HCl extractable) sediment fraction. Interestingly, the degree of MREE enrichment was significantly correlated with Ce anomalies (r2=0.72, P<0.001) and the heavy-REE (HREE) to light-REE (LREE) ratios (HREE/LREE, r2=0.74, P<0.001) in the reactive sediment fraction, only in those sites situated closest to the CASS drainage. The observed high MREE enrichments, positive Ce anomalies (>1) and HREE/LREE ratios (>1) are consistent with reactive Fe(III) oxides/oxyhydroxides driving REE retention in these sediments. This study indicates that CASS drainage alters REE signatures in receiving sediments by (1) providing a source of REEs, thereby enhancing sedimentary REE concentrations, and (2) causing accumulation of reactive Fe(III) phases with a high affinity for REEs. Together, these two factors drive the development of distinctive REE signatures in CASS-impacted sediments. The recognition of such signatures may provide a promising tool for identifying coastal sediments receiving anthropogenic CASS drainage inputs.

Rare earth elements concentrations and speciation in rainwater from Guiyang, an acid rain impacted zone of Southwest China

Rare earth elements (REEs) and major ions were determined in rainwater samples collected from Guiyang in the acid rain impacted zone of Southwest China. The concentrations of total dissolved and acid-soluble REEs in rainwater are higher than those of most of the world's cities as well as the local surface water. The dissolved REE concentrations are negatively correlated to pH in rainwater. This is consistent with acidification of rainwater resulting in increasing REE concentrations. Speciation calculations using the PHREEQC-Model predict that the free REE metal ion (i.e., Ln3+), sulfate (LnSO4+), oxalate (LnOx+ and LnOx2−) and fluoride (LnF2+) complexes were relatively important forms of dissolved REE. Although the contribution to rainwater acidity of oxalic acid is much lower than that of sulfuric acid, the proportion of REE-oxalate complexes is not lower than that of REE-sulfate complexes in rain waters. The rainwater is enriched in the middle REEs (MREE) compared to both the light REEs (LREE) and heavy REEs (HREE). REE-phosphate complexes, phosphatic minerals and a Fe-Mn-oxyhydroxide coating are more likely controls on the development of MREE enrichment in the rainwater. Complexation of sulfate and REE played little role in the development of MREE enrichment, even though sulfate is the most important anion in acidic rainwater. In the shale-normalized REE pattern plot, La showed a clear positive anomaly. La might have two main anthropogenic sources in rainwater. One of the important sources could be automobile emission; another main source of excess La in rainwater could be the REE fertilizer that has been widely used in the agriculture of China for approximately 30years.

The thermal and chemical evolution of hydrothermal vent fluids in shale hosted massive sulphide (SHMS) systems from the MacMillan Pass district (Yukon, Canada)

At Macmillan Pass (YT, Canada), the hydrothermal vent complexes beneath two shale-hosted massive sulphide (SHMS) deposits (Tom, Jason) are well preserved within Late Devonian strata. These deposits provide a unique opportunity to constrain key geochemical parameters (temperature, salinity, pH, fO2, ΣS) that are critical for metal transport and deposition in SHMS systems, and to evaluate the interaction between hydrothermal fluids and the mudstone host rock. This has been achieved using a combination of detailed petrography, isotopic techniques (δ34S, δ13C and δ18O values), carbonate rare earth element analysis (LA-ICP-MS), fluid inclusion analysis (microthermometry, gas analysis via incremental crush fast scan mass spectrometry), and thermodynamic modelling.Two main paragenetic stages are preserved in both vent complexes: Stage 1 comprises pervasive ankerite alteration of the organic-rich mudstone host rock and crosscutting stockwork ankerite veining (±pyrobitumen, pyrite and quartz) and; Stage 2 consists of main stage massive sulphide (galena-pyrrhotite-pyrite±chalcopyrite-sphalerite) and siderite (±quartz and barytocalcite) mineralisation. Co-variation of δ18O and δ13C values in ankerite can be described by temperature dependent fractionation and fluid rock interaction. Together with fluid inclusion microthermometry, this provides evidence of a steep thermal gradient (from 300 to ∼100°C) over approximately 15m stratigraphic depth, temporally and spatially constrained within the paragenesis of both vent complexes and developed under shallow lithostatic (<1km; 250 bars) to hydrostatic (<400m; 40 bars) conditions. There is evidence of mixing between diagenetic and hydrothermal fluids recorded in chondrite-normalised rare earth element (REE) profiles of ankerite and siderite. Middle REE enrichments and superchondritic Y/Ho ratios (>28), characteristic of diagenetic fluids, are coupled with positive europium anomalies and variable light REE depletion, which are more consistent with chloride complexation in hot (>250°C) hydrothermal fluids. In this shallow sub-seafloor setting, thermal alteration of organic carbon in the immature, chemically reactive mudstones also had an important role in the evolution of fluid chemistry. Reduced sulphur generation via thermochemical reduction of Late Devonian seawater sulphate produced positive δ34S values in sulphide minerals (+7.5‰ to +19.5‰), coupled with a suite of volatile components (CO2, CH4, C1–C4 hydrocarbons, N2) trapped in Stage 2 quartz.Many of these geochemical features developed during the final stages of fluid ascent, in a system where the fluid cooled close to the site of mineralisation. Using this information, we have modelled the metal transporting capacity of the deep hydrothermal fluid, which even at modest salinities (6wt.% NaCl) was high (≫100ppm Pb, Zn), owing to the combined effects of high temperature and low pH (⩽4.5). Therefore in SHMS systems, enhanced geothermal gradients and rapid fluid ascent (with minimal fluid cooling) are considered to be the most important factors for transporting high concentrations of base metals to the site of mineralisation.

Fluid source and methane-related diagenetic processes recorded in cold seep carbonates from the Alvheim channel, central North Sea

Integrated petrography, mineralogy, geochronology and geochemistry of cold seep carbonate crusts and free gas from the Alvheim channel elucidate diagenetic carbonate precipitation and related seepage histories in the central North Sea. Free gas isotope characteristics coupled with carbonate δ13C values as low as −66‰ VPDB, indicate a predominantly microbial methane source with minor thermogenic contribution. We estimate that ~70% of the carbon sequestered into carbonate precipitates was derived from local oxidation of methane. The early stage of crust growth is represented by microcrystalline aragonite and Mg-calcite (10 to 40% mol MgCO3) cementing seafloor sediments consisting of clays, quartz, feldspar, and minor detrital low Mg-calcite and dolomite. Typical association of aragonite cement with coarse-grained detritus may reflect elevated fluid flow and flushing of fine particles prior to cementation close to the seafloor. Middle rare earth element enrichment in early generation microcrystalline cements containing framboidal pyrite indicates diagenetic precipitation within the zone of anaerobic methane oxidation contiguous to iron reduction. The later generation diagenetic phase corresponds to less abundant radial fibrous and botryoidal aragonite which lines cavities developed within the crusts. In contrast to early generation cements, late generation cavity infills have rare earth elements and Y patterns with small negative Ce anomalies similar to seawater, consistent with carbonate precipitation in a more open, seawater dominated system. Aragonite U–Th ages indicate carbonate precipitation between 6.09 and 3.46kyr BP in the northern part of the channel, whereas in the southern part precipitation occurred between 1.94 and 0.81kyr BP reflecting regional changes in fluid conduit position.

Positive anomalous concentrations of Pb in some gabbroic rocks of Afikpo basin southeastern Nigeria.

Gabbroic rocks have intruded the sedimentary sequence at Ameta in Afikpo basin southeastern Nigeria. Petrographic and geochemical features of the rocks were studied in order to evaluate their genetic and geotectonic history. The petrographic results show that the rocks contain plagioclase, olivine, pyroxene, biotite, iron oxide, and traces of quartz in three samples. Major element characteristics show that the rocks are subalkaline. In addition, the rocks have geochemical characteristics similar to basaltic andesites. The trace elements results show inconsistent concentrations of high field strength elements (Zr, Nb, Th, Ta), moderate enrichment of large-ion lithophile elements (Rb, Sr, Ba) and low concentrations of Ni and Cr. Rare earth element results show that the rocks are characterized by enrichment of light rare earth elements, middle rare earth elements enrichment, and depletion of heavy rare earth elements with slight positive europium anomalies. Zinc concentrations are within the normal range in basaltic rocks. There are extremely high concentrations of Pb in three of the rock samples. The high Pb concentrations in some of these rocks could be as a result of last episodes of magmatic crystallization. The rocks intruded the Asu River Group; organic components in the sedimentary sequence probably contain Pb which has been assimilated into the magma at the evolutionary stage of the magma. Weathering of some rocks that contain galena could lead to an increase in the concentration of lead in the gabbroic rocks, especially when the migration and crystallization of magma take place in an aqueous environment. Nevertheless, high concentration of lead is hazardous to health and environment.

Diagenetic uptake of rare earth elements by conodont apatite

The rare earth element (REE) composition of bioapatite has long been used as a proxy for ancient seawater chemistry and paleomarine environmental reconstruction, based on the assumption of preservation of a hydrogenous (seawater-derived) REE signal. Recent work, however, has begun to question the provenance of REEs in conodonts, emphasizing the importance of REEs released by the lithogenous fraction of the sediment and subsequently adsorbed onto conodont apatite in the burial environment. Here, we investigate patterns of REE and trace-element abundance in conodonts and their host sediments from the Early to Late Ordovician Huanghuachang and Chenjiahe sections of Hubei Province, South China. Several lines of evidence indicate that REEs in the conodont samples were acquired mainly from clay minerals in the host sediment during burial diagenesis: (1) REEs in conodonts show a strong positive correlation to Th and other lithogenic elements; (2) conodonts and whole-rock samples show general patterns of REE and trace-element enrichment that are highly similar to each other and bear no resemblance to seawater elemental concentrations; (3) similar patterns are observed in Triassic conodonts and whole-rock samples; and (4) Y/Ho ratios in conodonts are mostly <40 (mean ~33), values that are consistent with derivation of >90% of REEs from lithogenous sources. Conodonts show pronounced middle rare earth element (MREE) enrichment, a pattern that is unambiguously of diagenetic origin owing to its association with lower Y/Ho ratios. With increasing MREE enrichment of conodont samples, U concentrations and LaN/YbN ratios shift from high to low, and Mn concentrations from low to high. These patterns suggest that conodont diagenesis was initiated at shallow burial depths under suboxic conditions (i.e., in the zone of Mn(IV) and Fe(III) reduction) but continued at greater burial depths, with most acquisition of secondary REEs at later diagenetic stages. Our findings indicate that (1) conodont apatite frequently does not preserve a recognizable hydrogenous REE signal, and (2) the results of many earlier studies in which REEs in bioapatite were used as a paleoseawater proxy may need re-evaluation.