Rare Earth Element Patterns in the Karst Terrains of Guizhou Province, China: Implication for Water/Particle Interaction

The authors determine the concentrations of dissolved (<0.22 μm) rare earth elements (REE) and suspended particulate matter (SPM) of typical karst rivers in Guizhou Province, China during the high-flow period. The concentrations of acid-soluble REE extracted from SPM using diluted hydrochloric acid are also obtained to investigate water/particle interaction in the river water. The dissolved REE contents in the river water are extremely low in the rivers of the study. The dissolved REE distribution patterns normalized by the Post Archean Australia Shale (PAAS) in the karst rivers are not flat, show slight enrichment of heavy REE to light REE, and also have significant negative Ce and Eu anomalies. The acid-soluble REE appears to have similar distribution patterns as characterized by MREE enrichment and slight LREE depletion, with unremarkable Ce and Eu anomalies. The PAAS-normalized REE distribution patterns of SPM are flat with negative Eu anomalies. The contents and distribution patterns of REE in the SPM are closely related to the lithological character of the source rocks. The SPM contains almost all the REE produced in the process of surficial weathering. This demonstrates that particle-hosted REE are the most important form of REE occurrence. REE fractionation, which takes place during weathering and transport, leads to an obvious HREE enrichment in the dissolved loads relative to the SPM. Y/Ho ratio can be used to shed light on REE behaviors during water/particle interaction.     

Rare earth geochemistry in the dissolved, suspended and sedimentary loads in karstic rivers, Southwest China

The watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) is a karstic area. Rare earth elements (REEs) of dissolved loads, suspended particulate material (SPM) and sediments of riverbed are first synthetically reported to investigate REE geochemistry in the three phases in karstic watershed during the high-flow season. Results show that the low dissolved REE concentrations in the CQW are attributed to these rivers draining carbonate rocks. The dissolved REE have significant negative Eu anomaly and coexistence of middle and light REE (MREE??PAAS-normalized La _N /Sm _N and Gd _N /Yb _N ; LREE??PAAS-normalized La _N /Yb _N )-enrichment, which are due to the dissolution of impure Triassic carbonates. REE concentrations in most of SPM exceed that of sediments in the CQW and the average continental crust (UCC). The SPM and the sediments show some common features: positive Eu, Ce anomalies, and MREE enrichment. The controls on the patterns seem to be from weathering profiles: the oxidation state, the REE-bearing secondary minerals (cerianite, potassium feldspar and plagioclase), which are also supported by the evidence of Y/Ho fractionations in the three phases.     

Dissolved rare earth elements in river waters draining karst terrains in Guizhou Province,China

Winter seasonal concentrations of dissolved rare earth elements (REE) of two major river systems (the Wujiang River system and the Yuanjiang River system) in karst-dominated regions in winter were measured by using a method involving solvent extraction and back-extraction and subsequent ICP-MS measurements. The dissolved REE concentrations in the rivers and their tributaries are lower than those in most of the large rivers in the world. High pH and high cation (i.e., Na⁺ + Ca²⁺) concentrations of the rivers are the most important factors controlling the concentrations of dissolved REE in the river water. The dissolved load (<0.22 μm) REE distribution patterns of high-pH river waters are very different from those of low-pH river waters. The shale (PAAS)-normalized REE patterns for the dissolved loads are characterized by light REE-enrichment and heavy REE-enrichment. Water in the upper reaches of the Wujiang River generally shows light REE-enriched patterns, while that in the middle and lower reaches generally shows heavy REE-enriched patterns. The Yuanjiang River is heavy REE enriched with respect to the light REE in the same samples. Water of the Wuyanghe River draining dolomite-dominated terrains has the highest heavy REE-enrichment. Most river water samples show the shale-normalized REE patterns with negative Ce and Eu anomalies, especially water from Wuyanghe River. Y/Ho ratios show that the water/particle interaction might have played an important role in fractionation between HREE and LREE.     

Behaviour of rare earth elements at the freshwater–seawater interface of two acid mine rivers: the Tinto and Odiel (Andalucia, Spain)

The concentrations of dissolved and suspended particulate rare-earth elements (REE) are reported in acid-sulphate waters from the Odiel and Tinto rivers. Shale normalized patterns are typically convex and high REE concentrations (e.g., Ce=0.43–65 μg.l⁻¹) are present in the waters. The REE content of the suspended load is greater by a factor of up to 3000. In the Odiel river, REE patterns of the particulates are essentially convex and sub-parallel to those of the waters; speciation calculations indicate that SO₄ complexes play a dominant role in controlling the REE distributions. In the Tinto river, the REE patterns of the suspended load are slightly fractionated and a negative Ce anomaly is apparent in several samples, reflecting the local influence of phosphogypsum deposits.Contrasting with normal estuaries, REE are not intensely removed in the low chlorinity zone. A remobilization in relation to Fe reduction is observed in the Tinto river.     

中国东部主要河流稀土元素地球化学特征

在2007年底至2008年初的枯水期间,系统采集了中国东部流域面积和径流量较大的33条河流沉积物、悬浮颗粒物和水样,采用等离子质谱法、X荧光光谱法等方法测定了14种稀土元素含量以及常量组分和水体pH值等理化指标。研究发现中国河流稀土元素浓度总体高于世界均值,且南方河流沉积物、悬浮物稀土元素含量高于北方河流,南方河流悬浮物态中稀土、重稀土呈现一定程度的相对富集,与我国上地壳稀土丰度和稀土矿产种类的南北分异相吻合。展示了以中国东部泥质岩稀土元素丰度标准化后的稀土配分模式及Ce、Eu异常特征,发现河流沉积物的中、重稀土元素相对富集,悬浮物轻稀土相对富集,溶解相重稀土富集的特征;北方河流溶解相稀土元素浓度明显大于南方河流,且除小清河外,溶解相Eu不同于沉积物与悬浮物而呈强烈的正异常,主要与河水理化性质影响下的稀土分异有关。研究发现小清河等少数河流沉积物中稀土元素为异常高值,经Al标准化处理、计算拟合剩余值后,认为小清河等河流稀土元素已受人为污染的影响。     

The aquatic chemistry of rare earth elements in rivers and estuaries

Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions.     

鄱阳湖流域赣江北支水体和沉积物中稀土元素的含量和分异特征

稀土的开发和广泛应用使得人们倍加关注其在环境中的分布及其环境地球化学行为。赣江作为鄱阳湖流域五大入湖河之一,发源于稀土资源富集的赣南地区,而其下游水体及周边地下水中稀土元素的含量和分异特征目前尚不完全清楚。以赣江北支水体及沉积物为研究对象,开展了稀土元素地球化学研究。结果表明,赣江北支水体中稀土元素总量在地表水中为230~1 146 ng/L(均值458.85 ng/L),地下水中为284~1 498 ng/L(均值634.94 ng/L),沉积物中稀土元素总量为177.9~270.7 mg/kg(均值226.99 mg/kg)。PHREEQC模拟计算表明,水体中的稀土元素主要以碳酸根络合物(REEC0₃⁺)的形式存在。地表水和地下水总体上均表现为重稀土元素相较于轻、中稀土元素富集,沉积物未表现出明显的富集特性;水体具有Ce、Eu负异常特点,而沉积物表现为Ce正异常和Eu负异常,指示氧化还原环境和水岩相互作用对稀土元素在水-沉积物系统中迁移转化的影响。地下水中稀土元素的含量沿流向具有上升趋势,而水体中重稀土元素的富集程度不断减弱,同时碳酸根络合物(REEC0₃⁺)的占比不断降低,反映水体中稀土元素的含量受到pH、胶体吸附、络合作用以及地下水-地表水相互作用的影响。水体中重稀土元素的富集受到碳酸根络合反应的影响,Ce、Eu负异常与Ce氧化沉淀和母岩特性相关。Gd异常值表明,研究区中下游水体中的Gd元素受到人为输入的影响。     

REE geochemistry of Early Cambrian phosphorites from Gezhongwu Formation at Zhijin, Guizhou Province, China

The Cambrian Gezhongwu Formation in Southwest China is the lowest Cambrian phosphorite unit. The Formation belongs to the Meishucun stage with small shelly fossils. Rare-earth element (REE)data from the Gezhongwu phosphorites of Zhijin documented the depositional conditions. The total REE concentrations are high in the Gezhongwu phosphorites, which are especially rich in yttrium. The PAASnormalized REE patterns of the Gezhongwu phosphorites are characterized by negative Ce anomalies and slight enrichment of MREE, as being hat-shaped. The hat-shaped patterns suggest that the REE originated from depositional environments rather than from subsequent diagenesis. The negative Ce anomalies indicate that the depositional environments are oxic. The positive Eu anomaly, the high total REE and the hatshaped REE pattern revealed contributions from the normal marine environment mixed with hydrothermal water to the REE budget of the Gezhongwu phosphorites.     

REE geochemistry of fine-grained sediments from major rivers around the Yellow Sea

To investigate the distribution pattern and controlling factors of rare earth elements (REEs) in riverine sediments, river mouth sediments were collected at five geographically different rivers around the Yellow Sea. Two- (1 M HCl leached and residual fractions) and five-step sequential extraction schemes (the SEDEX method) were applied to size-separated sediments < 20 µm. For the total REE composition, patterns normalized relative to the upper continental crust (UCC) showed light REE (LREE) and middle (MREE) enrichments in the Korean river sediments and MREE enrichment in the Chinese river sediments. LREE and MREE enrichments in 1 M HCl leached fractions played a major role in the distribution patterns of the total compositions in all the river sediments. About half of LREE enrichment in Korean river sediments was explained by the residual fraction. Comparison of the REE composition with major elements (Al, Fe, Ca, P) in each fraction of the SEDEX scheme revealed that MREE enrichment could be explained by reactive iron minerals, including goethite and hematite, although REE/Fe ratios showed different trends among the rivers due to different major REE-host iron minerals. After extracting reactive irons, authigenic phosphate, and carbonate, the sequential 1 M HCl fraction indicated that LREE enrichment in Korean river sediments may have originated from clay minerals, such as chlorite. These observations suggest that LREE enrichment may be a good tracer, while MREE enrichment should be used cautiously considering diagenetic modification, when using the REE composition to identify the sources of terrestrial materials.     

河流稀土元素地球化学研究进展

河流系统中,稀土元素(REE)受区域地质背景、风化作用、溶液化学以及水与颗粒物相互作用等因素的影响发生分异。河流悬浮物显示轻稀土(LREE)适度富集;河水显示重稀土(HREE)富集,或在HREE富集的基础上又有适度的中稀土(MREE)富集;与其它微量元素相比,REE在河水与颗粒物之间有较小的分配系数(K≈10-6);河流沉积物多显示平坦的REE配分模式。     

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.     

Zn isotopes in the suspended load of the Seine River, France: Isotopic variations and source determination

We report Zn isotopic ratios (δ⁶⁶Zn) of river suspended particulate matter (SPM) and floodplain deposits (FD) from the Seine basin, France, with a precision ?0.05‰. A decrease in δ⁶⁶Zn from 0.30‰ to 0.08‰ is observed in SPM from the upstream to downstream parts of the fluvial system, associated with an increase in Zn concentration from 100 ppm to 400 ppm. The Zn/Al of SPM at the river mouth is up to five times greater than the Zn/Al of the natural background, and by normalizing to the later value we define a Zn enrichment factor. Suspended sediments from a temporal series of samples collected in Paris display a similar variation in δ⁶⁶Zn of between 0.08‰ and 0.26‰, while showing an inverse relationship between the Zn enrichment factor and δ⁶⁶Zn. The amount of Zn transported as suspended load varies from 10% to 90%, as a function of increasing discharge. The δ⁶⁶Zn of SPM and the dissolved load are correlated, suggesting that adsorption processes are probably not the dominant process by which the Zn enrichment of SPM takes place. Instead, we interpret our data as reflecting the mixture of two main populations of suspended particles with distinct δ⁶⁶Zn. The first is characteristic of natural silicate particles transported by erosion processes to the river, while the second likely represents anthropogenic particles derived from wastewater treatment plants or combined sewer overflows. Based on isotopic ratios, we calculate that 70% of Zn in SPM of the Seine River in Paris is of anthropogenic origin.     

Geochemistry of rare-earth elements in thermal waters of Uzon-Geyzernaya hydrothermal system (Kamchatka)

Precisional analyses of the abundances of La, Ce, and major elements in thermal waters and rocks of the Uzon-Geyzernaya volcanotectonic depression, supplemented by published data on a number of modern high-temperature hydrothermal systems of Kamchatka and two other areas of the world, allowed defining genetically important patterns of rare-earth elements (REE) distribution. The La and Ce abundances positively correlate with silica contents both in fresh igneous rocks of the study areas and in the products formed by hydrothermal processes.All studied hydrothermal clays are enriched in La and Ce. The general enrichment trend is similar to the pattern of positive correlation between the La and Ce abundances. Geothermal waters display a strong relationship between REE enrichment and pH. Enhanced REE enrichment trend is observed in thermal waters with abundant SO₄^2 ? and K. The REE versus Cl and B diagrams show two individual fields reflecting the level of acidity-alkalinity of thermal waters. These data demonstrate that La and Ce concentrations in the products of modern hydrothermal systems (in fluids and secondary mineral phases) are governed by wallrock composition, anionic water composition, and pH/Eh-dependent adsorption processes.     

Geochemistry of rare-earth elements in shallow groundwater,northeastern Guangdong Province,China

Shallow groundwater and hot springs were collected from northeastern Guangdong Province, Southeast China, to determine the concentrations and fractionation patterns of rare-earth elements(REE). The results show that the La, Ce and Nd of REEs are abundant in groundwater and rock samples, and the ∑REE contents in groundwater and rock samples range from 126.5 to 2875.3 ng/L, and 79.44 to 385.85 mg/L, respectively. The shallow groundwater has slightly HREE-enriched PAAS-normalized patterns. However, the granitic rocks PAAS-normalized patterns, with remarkable negative Eu anomalies, are different from that of shallow groundwater. The enrichment of HREE is considered to be controlled by REE complexation and readsorption for most groundwater has Ce and Eu positive anomalies. The Ce and Eu anomalies in groundwater are controlled by redox conditions. Moreover, the Fe-contain sediments dissolution and/or the reduction of Fe oxyhydroxides are another factor contributing to Ce anomalies. The Eu anomalies in groundwater are controlled by the preferential mobilization of Eu2+ during water-rock interaction compared to Eu3+.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Rare earth elements in waters from the albitite-bearing granodiorites of Central Sardinia, Italy

With the aim of contributing to the knowledge of the geochemical behaviour and mobility of the rare earth element (REE) in the natural water systems, the ground and surface waters of the Ottana-Orani area (Central Sardinia, Italy) were sampled. The study area consists of albititic bodies included in Hercynian granodiorites. The waters have pH in the range of 6.0-8.6, total dissolved solid (TDS) of between 0.1 and 0.6 g/l, and major cation composition dominated by Ca and Na, whereas predominant anions are Cl and/or HCO₃.The pH and the major-element composition of the waters are the factors affecting the concentration of REE in solution. The concentrations of ∑REE+Y in the samples filtered at 0.4 μm vary between 140 and 1600 ng/l, with La of between 14 and 314 ng/l, and Yb of between <6 and 12 ng/l. A negative Ce anomaly, especially marked at high pH, is observed in the groundwaters. The surface waters show lower REE concentrations, which are independent of pH, and negligible Ce anomaly.Speciation calculations, carried out with the EQ3NR computer program, showed that the complexes with the CO₃²⁻ ligand are the dominant REE species at pH in the range of 6.7-8.6. The REE³⁺ ions dominate the speciation at pH <6.7 and only in the light REE (LREE).The relative concentrations of REE in water roughly reflect those in the aquifer host rocks. However, when concentrations of REE in water are normalised relative to the parent rocks, a preferential fractionation of heavy REE (HREE) into the water phase can be observed, suggesting the greater mobility and stability of HREE in aqueous solution.     

Geochemical behavior and speciation modeling of rare earth elements in acid drainages at Sarcheshmeh porphyry copper deposit,Kerman Province,Iran

Acid mine drainage is a major source of water pollution in the Sarcheshmeh porphyry copper mine area. The concentrations of heavy metals and rare earth elements (REEs) in the host rocks, natural waters and acid mine drainage (AMD) associated with mining and tailing impoundments are determined. Contrary to the solid samples, AMDs and impacted stream waters are enriched in middle rare earth elements (MREEs) and heavy rare earth elements (HREEs) relative to light rare earth elements (LREEs). This behavior suggests that REE probably fractionate during sulfide oxidation and acid generation and subsequent transport, so that MREE and HREE are preferentially enriched. Speciation modeling predict that the dominant dissolved REE inorganic species are Ln³⁺, Ln(SO₄)₂⁻, LnSO₄⁺, LnHCO₃²⁺, Ln(CO₃)₂⁻ and LnCO₃⁺. Compared to natural waters, Sarcheshmeh AMD is enriched in REEs and SO₄²⁻. High concentrations of SO₄²⁻ lead to the formation of stable LnSO₄⁺, thereby resulting in higher concentrations of REEs in AMD samples. The model indicates that LnSO₄⁺ is the dissolved form of REE in acid waters, while carbonate and dicarbonate complexes are the most abundant dissolved REE species in alkaline waters. The speciation calculations indicate that other factors besides complexation of the REE's, such as release of MREE from dissolution and/or desorption processes in soluble salts and poorly crystalline iron oxyhydroxy sulfates as well as dissolution of host rock MREE-bearing minerals control the dissolved REE concentrations and, hence, the MREE-enriched patterns of acid mine waters.     

Anthropogenic Rare Earth Element in rivers: Gadolinium and lanthanum. Partitioning between the dissolved and particulate phases in the Rhine River and spatial propagation through the Rhine-Meuse Delta (the Netherlands)

In this study, we report for the first time lanthanum and gadolinium anomalies at the catchment scale (Rhine-Meuse River system) together with the partitioning of their anthropogenic contents between the dissolved and the particulate phases. We compare the dissolved and total REE patterns of samples taken at 9 locations in the Rhine Branches including Lobith (situated at the German–Dutch border where the Rhine is not yet divided in three Branches), in surface water fed by the Rhine Branches (canals and lake IJsselmeer and Ketelmeer) and 3 locations where the water is derived from the river Meuse (originating from Belgium and France).We demonstrate that the anthropogenic input of lanthanum in the German part of the Rhine River identified by Kulaksiz and Bau (2011) can be traced in the complex Rhine-Meuse Delta up to the North Sea. In the Dutch Branches of the Rhine River, in contrast to the German part of the Rhine River, the anthropogenic lanthanum (La_ANTHRO) is mainly present in the particulate phase (SPM) and not in the dissolved phase (defined as the <0.45 μm fraction). In the Meuse River no anthropogenic lanthanum was found. The amount of La_ANTHRO transported by the Rhine River at the Lobith station (German–Dutch border) varies from 2008 to 2010 between 3.7 and 5.2 tons/y in the dissolved phase, and between 28.8 and 37.4 tons/y in the particulate phase. However, a big discrepancy is evidenced when we compare the La_ANTHRO load calculated on bases of the total water samples with the La_ANTHRO load calculated as the sum of the particulate and dissolved load: the total La_ANTHRO load is roughly 2 times larger than the La_ANTHRO load calculated as the sum of the dissolved and particulate La_ANTHRO load. The difference between the two calculated fluxes is most likely caused by not sampling the finest fraction of the particulate pool in the SPM samples with an overflow centrifuge.The anthropogenic gadolinium identified by high gadolinium anomalies in the REE patterns originates from numerous point sources (waste water treatment plant effluents) and can thus be considered as diffuse pollution when compared to anthropogenic lanthanum clearly resulting from a single source. The amount of anthropogenic gadolinium measured in the dissolved phase (main carrier of Gd) increases or decreases along the Rhine and Meuse Rivers depending whether or not the mixing water contains anthropogenic gadolinium, i.e. receives waste water effluents.     

Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau,East Sea

We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)_UCC, (La/Yb)_UCC, and (Ce/Ce^*)_UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce^*)_UCC ratios in the extractable fraction at depth.     

Distribution of rare earth elements in waters and bottom sediments of mineralized lakes in the eastern Transbaikal region (Russia)

Contents of rare earth elements in waters and bottom sediments are maximum in the most mineralized soda lakes. It is shown that REE occur in waters mainly as carbonate (LnСО₃)⁺ and oxyhydroxide LnO₂H, LnO⁺, (LnO₂)^– complexes, whose activity in the La → Lu series changes in opposite directions. It has been determined that increase of mineralization leads mainly to higher concentrations of the dissolved HREE. Prevalence of the absolute values of MREE and HREE is recorded in basins with the development of bacterial processes. Geochemical barrier for the accumulation of LREE in waters can be represented by fluorcarbonates, whose saturation degree in the soda lake waters can be several orders of magnitude higher than the solubility products (SP). Oxidative and reductive settings in lakes are favorable for the formation of Ce(OH)₄ and Ce(OH)₃, respectively.