Rare earth elements (REE) of dissolved and suspended loads in the Xijiang River, South China

The Xijiang River is the main channel of the Zhujiang (Pearl River), the second largest river in China in terms of water discharge, and flows through one of the largest carbonate provinces in the world. The rare earth element (REE) concentrations of the dissolved load and the suspended particulate matter (SPM) load were measured in the Xijiang River system during the high-flow season. The low dissolved REE concentration in the Xijiang River is attributed to the interaction of high pH and low DOC concentration. The PAAS-normalized REE patterns for the dissolved load show some common features: negative Ce anomaly, progressively heavy REE (HREE) enrichment relative to light REE (LREE). Similar to the world’s major rivers the absolute concentration of the dissolved REE in the Xijiang River are mainly pH controlled. The degree of REE partitioning between the dissolved load and SPM load is also strongly pH dependent. The negative Ce anomaly is progressively developed with increasing pH, being consistent with the oxidation of Ce (III) to Ce (IV) in the alkaline river waters, and the lack of Ce anomalies in several DOC-rich waters is presumably due to both Ce (III) and Ce (IV) being strongly bound by organic matter. The PAAS-normalized REE patterns for the dissolved load and the SPM load in rivers draining the carbonate rock area exhibit middle REE (MREE) enrichment and a distinct maximum at Eu, indicating the preferential dissolution of phosphatic minerals during weathering of host lithologies. Compared to the Xijiang River waters, the MREE enrichment with a maximum at Eu disappeared and light REE were more depleted in the South China Sea (SCS) waters, suggesting that the REE sourced from the Xijiang River must be further fractionated and modified on entering the SCS. The river fluxes of individual dissolved REE introduced by the Xijiang River into the SCS vary from 0.04 to 4.36 × 10⁴ mol a⁻¹.     

Rare earth elements in corals from the Isla de Sacrificios Reef,Veracruz, Mexico

Rare earth elements (REE) analysis was carried out in two coral species Diploria strigosa and Copophyllia natans from Isla de Sacrificios Reef (ISR) (19° 10′ 51.6″N; 96° 5′ 45.6″W) Veracruz, Mexico. Both corals were cut at the top, middle and bottom parts to detect possible differences in REE concentrations related to water masses and sediment inputs. An enrichment in heavy rare elements (HREE) compared to light rare elements (LREE) at the top of Diploria strigosa and Copophyllia natans, evidenced by (La/Lu)_SN <0.5, (La/Yb)_SN <0.5 and (Pr/Yb)_SN <0.5 is observed. This HREE enrichment in both corals is probably due to the high pH and CO₃^2? content in the seawater. A negative Ce anomaly is observed throughout Diploria strigosa and Copophyllia natans, probably linked with well oxygenated, highly oxidative modern shallow waters, and high nutrients related to suspended matter. Positive Eu anomalies in both corals are due to development of the ISR in shallow waters. Ce/Ce* vs. (Pr/Yb)_SN diagram suggests the input of terrigenous material, as all samples have Ce/Ce* and Pr/Yb values outside the seawater range signature. However, the Nd/Yb and (Nd/Yb)_SN suggest that the top of Diploria strigosa and Copophyllia natans are associated with coastal waters at about 50 m depth.     

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。     

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

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

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.     

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

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

Adsorption of REE(III)-humate complexes onto MnO2: Experimental evidence for cerium anomaly and lanthanide tetrad effect suppression

Experiments were conducted to evaluate the impact of organic complexation on the development of Ce anomalies and the lanthanide tetrad effect during the adsorption of rare-earth elements (REE) onto MnO₂. Two types of aqueous solutions—NaCl and NaNO₃—were tested at pH 5 and 7.5. Time-series experiments indicate that a steady-state is reached within less than 10 h when REE occur as free inorganic species, whereas steady state is not reached before 10 d when REE occur as REE-humate complexes. The distribution coefficients (K_d^REE) between suspended MnO₂ and solution show no or only very weak positive Ce anomaly or lanthanide tetrad effect when REE occur as humate complexes, unlike the results obtained in experiments with REE occurring as free inorganic species. Monitoring of dissolved organic carbon (DOC) concentrations show that log K_d^REE_organic/K_d^DOC ratios are close to 1.0, implying that the REE and humate remain bound to each other upon adsorption. Most likely, the Ce anomaly reduction/suppression in the organic experiments arises from a combination of two processes: (i) inability of MnO₂ to oxidize Ce(III) because of shielding of MnO₂ surfaces by humate molecules and (ii) Ce(IV) cannot be preferentially removed from solution due to quantitative complexation of the REE by organic matter. We suggest that the lack of lanthanide tetrad effect arises because the adsorption of REE-humate complexes onto MnO₂ occurs dominantly via the humate side of the complexes (anionic adsorption), thereby preventing expression of the differences in Racah parameters for 4f electron repulsion between REE and the oxide surface. The results presented here explain why, despite the development of strongly oxidizing conditions and the presence of MnO₂ in the aquifer, no (or insignificant) negative Ce anomalies are observed in organic-rich waters. The present study demonstrates experimentally that the Ce anomaly cannot be used as a reliable proxy of redox conditions in organic-rich waters or in precipitates formed at equilibrium with organic-rich waters.     

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.     

腾冲地热区高温热泉水中稀土元素特征

腾冲地热区位于印度-欧亚板块碰撞带东北缘,构造和岩浆活动频繁,地热作用明显,热泉广泛分布,是现代热泉研究的天然实验室。热泉水中的稀土元素特征是指示浅层水岩反应的重要指标。由于热泉水中稀土元素含量较低且变化范围大,腾冲地区热泉水稀土元素组成的报道比较罕见。本文尝试研究了腾冲高温热泉水中稀土元素组成特征,并与美国内华达州贝奥沃韦地热田和加利福尼亚希伯地热田热泉水的稀土元素特征进行了对比。本文选取腾冲地区的高温热泉,应用ICP-MS,测试了热泉水中稀土元素。分析结果表明热泉水中稀土元素含量相对较低且变化范围较大,其变化范围为球粒陨石的10-5～10-2倍。稀土元素球粒陨石标准化配分模式整体为轻微右倾型或平坦型,显示轻重稀土分异不明显;δEu既有正异常也有负异常;各热泉点热泉水稀土配分模式之间存在差异。虽然腾冲地热区热泉水的REE含量比美国贝奥沃韦地热田和希伯地热田热泉水的高10倍,两者之间的稀土元素分布特征具有一致性。热泉水中的δEu负异常为深循环的大气降水与具有负铕异常火山岩水岩反应的结果,正铕异常可能是由快速上返的大气降水与蒸发岩中的石膏反应导致。     

Rare earth element studies of surficial sediments from the southwestern Carlsberg Ridge,Indian Ocean

The rare earth element (REE) contents of sixteen surficial calcareous sediments from the southwestern Carlsberg Ridge, Indian Ocean, have been determined. The total REE vary from 35 ppm to 126 ppm and are inversely related to the calcium carbonate content. REEs show a strong positive correlation with Al + Fe + K + Mg + Na (r ²= 0.98) and Mn + Fe + Cu + Ni (r ²= 0.86) suggesting that the REE is associated with a combined phase of clays (mainly illite) and Mn-Fe oxyhydroxides. The aeolian input into these sediments is suggested from the weak positive Eu/Eu* anomaly. Shale-normalized (NASC) pattern along with La_(n)/Yb_(n) ratio suggest enrichment of heavy REE (HREE) relative to the light REE (LREE) with a negative Ce/Ce* anomaly implying retention of a bottom water REE pattern. An erratum to this article is available at .     

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.     

Rare earth elements,neodymium and strontium isotopic systematics in mineral waters: evidence from the Massif Central,France

Rare Earth Elements (REEs), and Sr and Nd isotope distributions, have been studied in mineralized waters from the Massif Central (France). The CO₂-rich springs are characterized by a neutral pH (6–7) associated with total dissolved solids (TDS) from 1 to 7 g l⁻¹. The waters result from the mixing of very mineralized water pools, thought to have equilibrated at a temperature of around 200°C with superficial waters. These two mineral water pools evidenced by Sr isotopes and dissolved REEs could reflect 2 different stages of water–rock interaction and an equilibrium with different mineral assemblages.The concentrations of individual dissolved REEs and total dissolved REEs (ΣREE), in the mineral waters examined, vary over several orders of magnitude but are not dependent on the main parameters of the waters (TDS, T°C, pH, Total Organic C). The dissolved REE concentrations presented as upper continental crust normalized patterns show HREE enrichment in most of the samples. The time evolution of REE patterns does not show significant fluctuations except in 1 borehole, located in the Limagne d’Allier area, which was sampled on 16 occasions over an 18 month period. Ten samples are HREE-enriched, whereas 6 samples show flat patterns.The aqueous speciation of REEs shows that CO²⁻₃ complexes dominate (>80%) over the free metal, F⁻, SO²⁻₄ and HCO⁻₃ complexes. The detailed speciation demonstrates that the fractionation of REEs (i.e. the HREE enrichment) in CO₂-rich and pH neutral fluids is due essentially to the predominance of the CO²⁻₃ complexes.The Sr isotopic composition of the mineral waters in the Massif Central shows different mixing processes; in the Cézallier area at least 3 end-member water types exist. The most dilute end-member is likely to originate as poorly mineralized waters with minimal groundwater circulation. Two other mineralized end-members are identified, although the link between the geographical location of spring outflow and the mixing proportion between the 2 end-members is not systematic. The range in ϵ_Nd(0) for mineralized waters in the Massif Central correlates well with that of the known parent rocks except for 4 springs. One way to explain the ϵ_Nd(0) in these instances is a contribution from drainage of volcanic rocks. The isotopic systematics help to constrain the hydrogeological models for this area.     

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.     

Competitive binding of REE to humic acid and manganese oxide: Impact of reaction kinetics on development of cerium anomaly and REE adsorption

The competitive binding of rare earth elements (REE) to purified humic acid (HA) and MnO₂ was studied experimentally using various HA/MnO₂ ratios over a range of pH (3 to 8). MnO₂, humic acid and REE solutions were simultaneously mixed to investigate the kinetics of the competitive reactions. Aqueous REE–HA complex is the dominant species whatever the experiment time, pH and HA/MnO₂ ratio. The value of the distribution coefficients between MnO₂ and solution (log K_d^Ree/Mno₂) increases with the HA/MnO₂ ratio, indicating that part of the REE–HA complexes are adsorbed onto MnO₂. The development of a Ce anomaly appears strongly limited in comparison with inorganic experimental conditions. Throughout the experimental run time, for HA/MnO₂ ratios of less than 0.4, MnO₂ acts as a competitor leading to a partial dissociation of the REE–HA complex. The majority of the dissociated REE is readsorbed onto the MnO₂ surface. The readsorption of REE is expressed by an increased Ce anomaly on the log K_d^Ree/Mno₂ pattern as well as a change in shape of the coefficient distribution of REE between soluble HA and solution pattern (log K_d^Ree/HA decrease for the heavy rare earth elements — HREE). Thus, REE are not only bound to MnO₂ as a REE–HA complex, but also as REE(III). Moreover, the competition between HA and MnO₂ for REE binding is shown to be higher at low pH (< 6) and low DOC/Mn ratio. This study partially confirms previous work that demonstrated the control of REE adsorption by organic matter, while shedding more light on the impact of pH as well as complexation reaction competition on long-term REE partitioning between solid surface and organic solutions. The latter point is important as regards to REE speciation under conditions typical of rock and/or mineral alteration.     

Rare-earth elements in groundwaters from the Osamu Utsumi mine and Morro do Ferro analogue study sites, Poços de Caldas, Brazil

Data are presented on rare-earth elements (REE) in prefiltered (<450 nm) near-surface and deeper groundwaters and in corresponding particulate matter (>450 nm) from the Osamu Utsumi uranium mine and the Morro do Ferro thorium-REE-deposit. Groundwaters from both sites typically contain between 1–50 μg/l of total REE, but can reach values of up to 160 μg/l in the deepest borehole F4 (U-Mine: 150–415 m). Even higher REE concentrations of up to 29 mg/l were measured in acidic, sulfate-rich near-surface waters of the same site. The chondrite-normalized REE patterns in deeper, more reducing groundwaters and in their corresponding suspended particle fractions are similar to those observed in the bedrock (phonolites), indicating that bedrock leaching and secondary mineral sorption occurred without significant fractionation between these elements, in accordance with the only small variations in the stability constants of the expected REE-sulfate complexes in these waters. Groundwaters from the unsaturated zone of both sites show a very characteristic cerium depletion (less pronounced than that observed in the corresponding suspended particulate fractions), which is most probably related to the oxidation of Ce (III) under the prevailing E_h-conditions of these waters (600 to 800 mV), and to sorption/precipitation reactions of the much less soluble Ce(IV) species. Coarse particulate matter (>450 nm), composed mainly of amorphous ferric hydrous oxides, has a strong capacity for sorption of REE. This is shown by its very high REE concentrations, in some boreholes > 8,000 μg/g (total REE), and by the calculated association ratios R_a (ml/g), which are in the order of 10⁵ to 10⁶. The implications of these findings for the migration behavior of REE in both environments are discussed.     

Mineralogical control of rare earth elements in acid sulfate soils

Major, trace and rare earth element concentrations were measured in porewater, surface water and sediments at an acid sulfate soil site. The concentrations of La and Ce in porewater are up to 1-3 ppm. There is a strong correlation between REE concentration and acidity, except that the maximum concentrations were consistently found below the horizon of maximum acidity, associated with an increase in pH (to ca. 4) and change in mineralogy from jarosite-dominated to goethite-dominated mottles. Jarosite replacement by goethite is as expected with the rise in pH, which in turn is due to the occurrence of a fossil shell bed just below. The rare earth element patterns in the porewaters are enriched in the MREE with respect to Post-Archaean Australian Shale (PAAS). Measurements and calculations show that this is in accord with experiments on low-degree partial dissolution of jarosite, even when the jarosite itself is highly enriched in LREE. There is a clear fractionation in the patterns between the clay-rich soil matrix, which is slightly depleted in the LREE when normalized to PAAS (La/Yb_PAAS ∼0.5), and the secondary mineral phase jarosite, which is enriched in the LREE (La/Yb_PAAS = 15-50). The REE pattern in the porewater changes with the transition from jarosite- to goethite-rich mottles, becoming relatively more enriched in the LREE compared to the HREE, which is consistent with the incongruent dissolution of jarosite to form goethite and the release of greater amounts of jarosite REE to solution, including proportionately more of the jarosite-compatible LREE.Maximum surface water REE concentrations in acidic water were 100-200 ppb La and Ce. REE patterns in surface water were very similar to the porewater transition zone, enriched in the MREE, but asymmetric, relatively enriched in the LREE compared to the HREE.     

Experimental Study on the Effects of Organic Acids on the Dissolution of REE in the Weathering Crust of Granite

The results of REE leached by some organic acids with various concentrations and water/rock ratios for different durations from a mixed samples of the weathering crust of a granite in Gonghe,Guangdong,China,showed that:1)the contents of REE leached increase with increasing concentrations of the organic acids;2) the contents of REE leached by 0.01mol/L organic acids increase with increasing water/rock ration;3) the interaction between the organic acids and the samples enhances the pH value of the medium and the contents of REE leached tend to increase with decreasing pH value;and 4) compared with those leached by ammonia sulfate,the REE leached by the organic acids are characterized by a weaker negative C e anomaly,a stronger negative Eu anomaly,and lower(La/Sm)N and (Gd/Yb)N ratios,indicating that the organic acids have made contributions to the fractionation of REE in the weathering crust.     

REE and Sr isotope characteristics of carbonate within the Cu–Co mineralized sedimentary sequence of the Nchanga Mine,Zambian Copperbelt

Carbonate, largely in the form of dolomite, is found throughout the host rocks and ores of the Nchanga mine of the Zambian Copperbelt. Dolomite samples from the hanging wall of the mineralization show low concentrations of rare-earth elements (REE) and roof-shaped, upward convex, shale-normalized REE patterns, with positive Eu*_SN anomalies (1.54 and 1.39) and marginally negative Ce anomalies (Ce*_SN 0.98,0.93). In contrast, dolomite samples associated with copper and cobalt mineralization show a significant rotation of the REE profile, with HREE enrichment, and La/Lu_SN ratios <1 (0.06–0.42). These samples also tend to show variable but predominantly negative Eu*_SN and positive cerium anomalies and an upwardly concave MREE distribution (Gd-Er). Malachite samples from the Lower Orebody show roof-tile-normalized REE patterns with negative europium anomalies (Eu*_SN 0.65–0.80) and negative cerium anomalies (Ce*_SN 0.86–0.9). The carbonate ⁸⁷Sr/⁸⁶Sr signature correlates with the associated REE values. The uppermost dolomite samples show Neoproterozoic seawater-like ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7111 to 0.7116, whereas carbonate from Cu–Co mineralized samples show relatively low concentrations of strontium and more radiogenic ⁸⁷Sr/⁸⁶Sr, ranging between 0.7136–0.7469. The malachite samples show low concentrations of strontium, but give a highly radiogenic ⁸⁷Sr/⁸⁶Sr of 0.7735, the most radiogenic ⁸⁷Sr/⁸⁶Sr ratio. These new data suggest that the origin and timing of carbonate precipitation at Nchanga is reflected in the REE and Sr isotope chemistry. The upper dolomite samples show a modified, but essentially seawater-like signature, whereas the rotation of the REE profile, the MREE enrichment, the development of a negative Eu*_SN anomaly and more radiogenic ⁸⁷Sr/⁸⁶Sr suggests the dolomite in the Cu–Co mineralized samples precipitated from basinal brines which had undergone significant fluid–rock interaction. Petrographic, REE, and ⁸⁷Sr/⁸⁶Sr data for malachite are consistent with the original sulfide Lower Orebody being subject to a later oxidizing event.     

Rapid development of negative Ce anomalies in surface waters and contrasting REE patterns in groundwaters associated with Zn–Pb massive sulphide deposits

Ground and surface waters collected from two undisturbed Zn–Pb massive sulphide deposits (the Halfmile Lake and Restigouche deposits) and active mines in the Bathurst Mining Camp (BMC), NB, Canada were analysed for the rare earth elements (REE). REE contents are highly variable in waters of the BMC, with higher contents typical of waters with higher Fe and lower pH. There are significant differences between ground- and surface waters and between groundwaters from different deposits. The REE contents of surface waters are broadly similar within and between deposit areas, although there are spatial variations reflecting differences in pH and redox conditions. Surface waters are characterised by strong negative Ce anomalies ([Ce/Ce*]_NASC as low as 0.08), produced by oxidation of Ce³⁺ to Ce⁴⁺ and preferential removal of Ce⁴⁺ from solution upon leaving the shallow groundwater environment. Groundwaters and seeps typically lack significant Ce anomalies reflecting generally more reducing conditions in the subsurface environment and indicating that Ce oxidation is a rapid process in the surface waters. Deeper groundwaters at the Halfmile Lake deposit are characterised by REE patterns that are similar to the host lithologies, whereas most groundwaters at the Restigouche deposit have LREE-depleted patterns compared to NASC. Halfmile Lake deposit groundwaters have generally lower pH values, whereas Restigouche deposit groundwaters show greater heavy REE-complexation by carbonate ions. Shallow waters at the Halfmile Lake and Stratmat Main Zone deposits have unusual patterns which reflect either the adsorption of light REE onto colloids and fracture-zone minerals and/or precipitation of REE–phosphate minerals. Middle REE-enrichment is typical for ground- and surface waters and is highest for neutral pH waters. The labile portion of stream sediments are generally more middle REE-enriched than total sediment and surface waters indicating that the REE are removed from solution by adsorption to Fe- and Mn-oxyhydroxides in the order middle REE≥light REE>heavy REE.