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.     

Partition coefficients for REE between garnets and liquids: implications of non-Henry's Law behaviour for models of basalt origin and evolution

Partition coefficients for the rare earth elements (REE) Ce, Sm and Tm between coexisting garnets and hydrous liquids have been determined at high pressure and temperatures (30 kbar and 1300 and 1500°C). Two synthetic systems were studied, Mg₃Al₂Si₃O₁₂-H₂O and Ca₃Al₂Si₃O₁₂-H₂O, in addition to a natural pyrope-bearing system.Deviations from Henry's Law behaviour occur at geologically relevant REE concentrations. At concentrations < 3 ppm Ce, < 12 ppm Sm, < 80 ppm Tm in pyrope and < 100 ppm Ce, < 250 ppm Sm, < 1000 ppm Tm in grossular (at 30 kbar and 1300°C), D^{garnet liquid}_REE increases as the REE concentration in the garnet decreases. At higher concentrations, D_REE is constant. D^{grossular liquid}_REE also constant when the garnet contains less than about 2 ppm Sm or Tm. The REE concentration at which D_REE becomes constant increases with increasing temperature, decreasing REE ionic radius and increasing Ca content of the garnet.Partitioning behaviour of Ce, Sm and Tm between a natural pyrope-rich garnet and hydrous liquid is analogous to that in the synthetic systems and substantiates the substitution model proposed by Harrison and Wood (1980).Values of D_REE^{garnet/liquid} for which Henry's Law is obeyed are systematically higher for grossular than for pyrope (D^{pyrope/liquid} = 0.067(Ce), 0.108(Sm), 0.155(Tm) and D^{grossular/Liquid} = 0.65(Ce), 0.75(Sm), 4.55(Tm).The implications of non-Henry's Law partitioning of REE for models of basalt petrogenesis involving garnet are far-ranging. Deviations from Henry's Law permit refinements to be made to calculated REE abundances once basic model parameters have been defined.     

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.     

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.     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.     

Geochemical and hydrogeochemical evolution of groundwater in Ferdows area, northeast of Iran

The chemical analysis of 19 water wells in Ferdows area, Northeastern Iran, has been evaluated to determine the hydrogeochemical processes and ion concentration background in the region. In the study area, the order of cation and anion abundance is Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and Cl^? > SO ₄ ^?2  > HCO₃ ^? > NO₃ ^?, respectively, and the dominating hydrochemical types are Na–Cl. Most metal concentrations in water depend on the mineral solubility, and pH, Eh, and salinity of the solution. Their ΣREE concentrations showed excellent correlations with parameters such as TDS and pH. North American Shale Composite (NASC)-normalized REE patterns are enriched in the HREEs relative to the LREEs for all groundwaters. They all have positive Eu anomalies (Eu/Eu* = 0.752–3.934) and slightly negative Ce anomalies (Ce/Ce* = 0.019–1.057). Reduction–oxidation, complexation, desorption, and re-adsorption alter groundwater REE concentrations and fractionation patterns. The positive Eu anomalies in groundwaters are probably due to preferential mobilization of Eu²⁺ relative to the trivalent REEs in the reducing condition.     

The solubility of iron hydroxide in sodium chloride solutions

The solubility of iron(III) hydroxide as a function of pH was investigated in NaCl solutions at different temperatures (5–50°C) and ionic strengths (0–5 M). Our results at 25°C and 0.7 M in the acidic range are similar to the solubility in seawater. The results between 7.5 to 9 are constant (close to 10⁻¹¹ M) and are lower than those found in seawater (>10⁻¹⁰) in this pH range. The solubility subsequently increases as the pH increases from 9 to 12. The solubility between 6 and 7.5 has a change of slope that cannot be accounted for by changes in the speciation of Fe(III). This effect has been attributed to a solid-state transformation of Fe(OH)₃ to FeOOH. The effect of ionic strength from 0.1 to 5 M at a pH near 8 was quite small. The solubility at 5°C is considerably higher than at 25°C at neutral pH range. The effects of temperature and ionic strength on the solubility at low and high pH have been attributed to the effects on the solubility product and the formation of FeOH²⁺ and Fe(OH)₄⁻. The results have been used to determine the solubility products of Fe(OH)₃, K¹_Fe(OH)3 and hydrolysis constants, β¹₁, β¹₂, β¹₃, and β¹₄ as a function of temperature (T, K) and ionic strength (I):log K¹_Fe(OH)3 = −13.486 − 0.1856 I^0.5 + 0.3073 I + 5254/T (σ = 0.08)log β¹₁ = 2.517 − 0.8885 I^0.5 + 0.2139 I − 1320/T (σ = 0.03)log β¹₂ = 0.4511 − 0.3305 I^0.5 − 1996/T (σ = 0.1)log β¹₃ = −0.2965 − 0.7881 I^0.5 − 4086/T (σ = 0.6)log β¹₄ = 4.4466 − 0.8505 I^0.5 − 7980/T. (σ = 0.2)Both strong ethylenediaminetetraacetic acid and weak (HA) organic ligands greatly affect iron solubility. The additions of ethylenediaminetetraacetic acid and humic material were shown to increase the solubility near pH 8. The higher solubility of Fe(III) in seawater compared to 0.7 M NaCl may be caused by natural organic ligands.     

The REE species and their distribution in ferromanganese crusts in the Sea of Japan

Polished sections of ferromanganese crusts on underwater rises in the Sea of Japan were studied with a JXA8100 microprobe analyser. Mineral phases of REE have been detected. They have Ln₂O₃ chemical composition, where Ln is La–Ce–Pr–Nd, La–Ce–Nd, or, much more rarely, La–Ce and La–Ce–Pr. With regard to the same chemical composition of REE grains in the ore crusts and basalts from Medvedev Volcano, it has been concluded that these REE were supplied during postvolcanic gas–hydrothermal processes.     

Metal loading effect on rare earth element binding to humic acid: Experimental and modelling evidence

The effect of metal loading on the binding of rare earth elements (REE) to humic acid (HA) was studied by combining ultrafiltration and Inductively Coupled Plasma Mass Spectrometry techniques. REE-HA complexation experiments were performed at pH 3 for REE/C molar ratios ranging from ca 4 × 10⁻⁴ to 2.7 × 10⁻². Results show that the relative amount of REE bound to HA strongly increases with decreasing REE/C. A middle-REE (MREE) downward concavity is shown by patterns at high metal loading, whereas patterns at low metal loading display a regular increase from La to Lu. Humic Ion Model VI modelling are close to the experimental data variations, provided that (i) the ΔLK₂ parameter (i.e. the Model VI parameter taken into account the presence of strong but low density binding sites) is allowed to increase regularly from La to Lu (from 1.1 to 2.1) and (ii) the published log K_MA values (i.e. the REE-HA binding constants specific to Model VI) are slightly modified, in particular with respect to heavy REE. Modelling approach provided evidence that patterns with varying REE/C likely arises because REE binding to HA occurs through two types of binding sites in different density: (i) a few strong sites that preferentially complex the heavy REE and thus control the atterns at low REE/C; (ii) a larger amount of weaker binding sites that preferentially complex the middle-REE and thus control the pattern at high REE/C. Hence, metal loading exerts a major effect on HA-mediated REE binding, which could explain the diversity of published conditional constants for REE binding with HA. A literature survey suggests that the few strong sites activated at low REE/C could be multidentate carboxylic sites, or perhaps N-, or P-functional groups. Finally, an examination of the literature field data proposed that the described loading effect could account for much of the variation in REE patterns observed in natural organic-rich waters (DOC > 5 mg L⁻¹ and 4 ? pH ? 7).     

The effect of tissue structure and soil chemistry on trace element uptake in fossils

Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H₂O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO₃. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element “plumes” down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ∼5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients (K_d’s). Although acid leaches and bulk digestion of soils yield comparable fossil-soil K_d’s among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H₂O leachates instead reveal radically different K_d’s in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE K_d’s and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading K_d’s for many trace elements, especially the REE, and H₂O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.     

REE mineralogy and geochemistry of the Western Keivy peralkaline granite massif,Kola Peninsula,Russia

The authors have studied the geology, geochemistry, petrology and mineralogy of the rare earth elements (REE) occurring in the Western Keivy peralkaline granite massif (Kola Peninsula, NW Russia) aged 2674 ± 6 Ma. The massif hosts Zr- and REE-rich areas with economic potential (e.g. the Yumperuaiv and Large Pedestal Zr-REE deposits), where 25% of ΣREE are represented by heavy REE (HREE). The main REE minerals are: chevkinite-(Ce), britholite-(Y) and products of their metamict decay, bastnäsite-(Ce), allanite-(Ce), fergusonite-(Y), monazite-(Ce), and others. The areas contain also significant quantities of zircon reaching potentially economic levels. We have discovered that behavior of REE and Zr is controlled by alkalinity of melt/solution, which, in turn, is controlled by crystallization of alkaline pyroxenes (predominantly aegirine) and amphiboles (predominantly arfvedsonite) at a late magmatic stage. Crystallization of mafic minerals leads to a sharp increase of K₂O content and decrease of SiO₂ content that cause a decrease of melt viscosity and REE and Zr solubility in the liquid. Therefore, REE and zirconium immediately precipitate as zircon and REE-minerals. There are numerous pod- and lens-like granitic pegmatites within the massif. Pegmatites in the REE-rich areas are also enriched in REE, but HREE prevails over light REE (LREE), about 88% of REE sum.     

Surface-structure-controlled sectoral zoning of the rare earth elements in fluorite from Long Lake, New York, and Bingham, New Mexico, USA

The concentration and distribution of rare earth elements (REE) in sectorally zoned fluorite crystals from Long Lake, New York, and the Hansonburg Mining District, Bingham, New Mexico, have been studied using cathodoluminescence and synchrotron X-ray fluorescence microanalysis (SXRFMA). In cubo-octahedral samples from Long Lake, New York, Ce, Nd, Gd, Dy, Ho, Er, and Tm are preferentially partitioned into the |111| sector relative to the |100| sector. Partition coefficients (K_d = concentration in |111| sector/concentration in |100| sector) range between 3.5 for Ce, to 1.4 for Tm, with a general decrease in K_d as elements deviated from the ionic radius of Ca²⁺, for which REE substitute in fluorite. Diffusion of the REE has occurred, as evidenced by gradual changes in composition over distances of 0.2 to 0.3 mm at sector boundaries.In Bingham samples, three different partition coefficients were determined for Dy: K_d|100|/|111| = 2.83, K_{d |100|/|110|} = 1.77, and K_{d |110|/|111|} = 1.60. These are mean K_d values for a 95% confidence interval. In another sample from the same deposit, Dy, Er, and Gd were found to be preferentially incorporated into the |100| sector relative to the |210| sector with average K_{d |100|/|210|} of 3.1, 2.4, and 2.9, respectively. In a third sample, Nd was found to be preferentially incorporated into the |110| sector relative to the |321| sector with an average K_{d |110|/|321|} value of 2.3.Compositional heterogeneities in a given sector (concentric zoning) have been resolved using SXRFMA but are significantly less than the concentration difference across sector boundaries. Often fluorite exists in a wide variety of morphologies, as is the case in the Hansonburg Mining District of Bingham. We suggest caution when using the REE as petrogenetic indicators because fluorite trace element chemistry can vary greatly among crystals within a deposit depending on the internal morphology of a particular crystal.     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

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.     

Sorption of selenite in a multi-component system using the “dialysis membrane” method

⁷⁹Se is a potentially mobile long-lived fission product, which may make a dominant contribution to the long-term radiation exposure resulting from deep geological disposal of radioactive waste. Its mobility is affected by sorption on minerals. Selenium sorption processes have been studied mainly by considering interaction with a single mineral surface. In the case of multi-component systems (e.g. soils), it is difficult to predict the radioelement behaviour only from the mineral constituents. This study contributes to the understanding of multi-component controls of Se concentrations towards predicting Se behaviour in soils after migration from a disposal site. This goal was approached by measuring selenite sorption on mono and multi-phase systems physically separated by dialysis membranes. To the best of the authors’ knowledge, very few studies have used dialysis membranes to study the sorption competition of selenite between several mineral phases. Other workers have used this method to study the sorption of pesticides on montmorillonite in the presence of dissolved organic matter. Indeed, this method allows measurement of individual K_d in a system composed of several mineral phases. Dialysis membranes allowed (i) determination of the competition of two mineral phases for selenite sorption (ii) and determination of the role of humic acids (HAs) on selenite sorption in oxidising conditions. Experimental results at pH 7.0 show an average Se(IV) sorption distribution coefficient (K_d) of approximately 125 and 9410 L kg⁻¹ for bentonite and goethite, respectively. The average K_d for goethite decreases to 613 L kg⁻¹ or 3215 L kg⁻¹ in the presence of bentonite or HA, respectively. For bentonite, the average K_d decreases slightly in the presence of goethite (60 L kg⁻¹) and remains unchanged in the presence of HA. The experimental data were successfully modelled with a surface complexation model using the PHREEQC geochemical code. The drastic decrease in Se(IV) sorption on goethite in a multi-phase system is attributed to competition with dissolved silica released by bentonite. As with Si the HA compete with Se for sorption sites on goethite.     

Lanthanide-humic substances complexation. I. Experimental evidence for a lanthanide contraction effect

The interaction of the lanthanides (Ln) with humic substances (HS) was investigated with a novel chemical speciation tool, Capillary Electrophoresis-Inductively Coupled Plasma Mass Spectrometry (CE-ICP-MS). By using an EDTA-ligand competition method, a bi-modal species distribution of LnEDTA and LnHS is attained, separated by CE, and detected online by sector field ICP-MS. We quantified the binding of all 14 rare earth elements (REEs), Sc and Y with Suwannee river fulvic acid, Leonardite coal humic acid, and Elliot soil humic acid under environmental conditions (pH 6-9, 0.001-0.1 mol L⁻¹ NaNO₃, 1-1000 nmol L⁻¹ Ln, 10-20 mg L⁻¹ HS). Conditional binding constants for REE-HS interaction (K_c) ranged from 8.9 < log K_c < 16.5 under all experimental conditions, and display a lanthanide contraction effect, Δ_LK_c: a gradual increase in K_c from La to Lu by 2-3 orders of magnitude as a function of decreasing ionic radius. HS polyelectrolyte effects cause K_c to increase with increasing pH and decreasing ionic strength. Δ_LK_c increases significantly with increasing pH, and likely with decreasing ionic strength. Based on a strong correlation between Δ_LK_c values and denticity for organic acids, we suggest that HS form a range of tri- to tetra-dentate complexes under environmental conditions. These results confirm HS to be a strong complexing agent for Ln, and show rigorous experimental evidence for potential REE fractionation by HS complexation.     

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.     

Sedimentary humic acid and fulvic acid as surface active substances

Surface tension of sedimentary fulvic acid (FA) and humic acid (HA) with molecular weight from < 10,000 to > 300,000 was measured at 5°C and 25°C, over a wide range of concentrations (0.114-107.4 g/l) at pH 8. HA was in the form of sodium humate. Surface tension decreases with an increase in HA and FA concentration and both HA and FA were found to be surface active materials with FA exhibiting the lowest surface tension (31 dynes/cm).Plots of surface tension vs. log concentration gave two straight lines with a break at a certain concentration similar to surfactants. From the concentration at the break point, aggregation concentration (AGC) was determined. For HA with molecular weight above 10,000, the AGC decreased with an increase in molecular weight. The more hydrophobic the HA, the greater was the tendency to form aggregates. Surface excess (surface concentration) was determined (2.3 × 10^?10?5.5 × 10^?10mol/cn²) from the slope of the plot of surface tension vs. log concentration for concentrations lower than the AGC. Adsorption of HA into the surface layer increased with increasing molecular weight of HA.     

Contrasting geochemical and Sm-Nd isotopic compositions of Archean metasediments from the Kongling high-grade terrain of the Yangtze craton: evidence for cratonic evolution and redistribution of REE during crustal anatexis

Twenty-three clastic metasediments from the Kongling high-grade terrain of the Yangtze craton, South China were analyzed for major, trace and rare earth elements and Sm-Nd isotopic ratios. Associated dioritic-tonalitic-trondhjemitic (DTT) and granitic gneisses as well as amphibolites were also analyzed in order to constrain provenance. The results show that the clastic metasediments can be classified into 3 distinct groups in terms of mineralogical, geochemical and Sm-Nd isotopic compositions. Group A is characterized by having no to slight negative Eu anomalies (Eu/Eu1 = 0.82–1.07), being high in Cr (191–396 ppm) and Ni (68–137 ppm), and low in Th (3.3–7.8 ppm) and REE (ΣREE = 99–156 ppm). These characteristics are similar to those of metasediments from Archean greenstone belts. In addition, the Group A metasediments have the value of the Chemical Index of Alteration (CIW) close to felsic gneisses. Their Sm-Nd isotopic, REE and trace element compositions can be interpreted by mixtures of the DTT gneisses and amphibolites. Dating of detrital zircons from 2 Group A samples by SHRIMP reveals a major concordant age group of 2.87–3.0 Ga, which is identical to the age of the trondhjemitic gneiss. These results strongly suggest that Group A was principally the first-cycle erosion product of the local Kongling DTT gneiss and amphibolite. Moreover, the higher than amphibolite Cr content and slight Eu depletion exhibited by some samples from this group infer that ultramafic rocks like komatiite and granite of probably 3.0–3.3 Ga in age also played a role.Group B is characterized by the presence of graphite and shows a more evolved composition similar to post-Archean shales with a prominent negative Eu anomaly (Eu/Eu1 = 0.48–0.77) and high CIW. On paired Cr/Th vs La/Co and Co/Th plots, Group B samples conform to a two-end member mixing line of the Kongling granitic gneiss and amphibolite. However, data on Nd model age and CIW suggest that the granite component should be younger than the sampled granitic gneiss and derived from a distal source.Both Groups A and B exhibit a clear positive correlation between CIW and T_DM and a negative one between CIW and Eu/Eu1. These correlations point to the crustal evolution of the Yangtze craton towards coupled increasing CIW and Eu depletion with decreasing age. This in turn reflects the change of granitoid magmatism from local Na-rich dioritic-tonalitic-trondhjemitic rocks to widespread K-feldspar granite. The change led to the intracrustal differentiation, stabilization and growth of the craton.Group C is restite and contains abundant sillimanite and garnet and unusually high ilmenite (7–11vol%), which can be seen to be dehydration melting products of biotite under the microscope. This group shows extremely varied REE distributions from LREE enriched to depleted and from negative to strong positive (Eu/Eu1 = 1.63) Eu anomalies. Compared to Groups A and B, Group C is severely depleted in Na₂O, K₂O, LREE, Rb and Ba, whereas TiO₂, Co, V, Sc and HREE and Y are considerably enriched. This is accompanied by anomalous high Sm/Nd (0.21–0.28), ¹⁴⁷Sm/¹⁴⁴Nd (0.1361–0.1738) and ¹⁴³Nd/¹⁴⁴Nd (0.511589–0.511958) ratios. T_DM correlates clearly with Sm/Nd ratio and 2 out of 3 samples give significantly older to unrealistic T_DM (3.9–4.9 Ga). The results document redistribution of REE and an open behavior of the Sm-Nd isotope system during the biotite dehydration melting of metasediments.     

Surface chemistry and relative Ni sorptive capacities of synthetic hydrous Mn oxyhydroxides under variable wetting and drying regimes

The surface binding site characteristics and Ni sorptive capacities of synthesized hydrous Mn oxyhydroxides experimentally conditioned to represent three hydrological conditions—MnO_XW, freshly precipitated; MnO_XD, dried at 37°C for 8 d; and MnO_XC, cyclically hydrated and dehydrated (at 37°C) over a 24-h cycle for 7 d—were examined through particle size analysis, surface acid-base titrations and subsequent modelling of the pK_a spectrum, and batch Ni sorption experiments at two pH values (2 and 5). Mineralogical bulk analyses by XRD indicate that all three treatments resulted in amorphous Mn oxyhydroxides; i.e., no substantial bulk crystalline phases were produced through drying. However, drying and repeated wetting and drying resulted in a non-reversible decrease in particle size. In contrast, total proton binding capacities determined by acid-base titrations were reversibly altered with drying and cyclically re-wetting and drying from 82 ± 5 μmol/m² for the MnO_XW to 21 ± 1 μmol/m² for the MnO_XD and 37 ± 5 μmol/m² for the MnO_XC. Total proton binding sites measured decreased by ≈75% with drying from the MnO_XW and then increased to ≈50% of the MnO_XW value in the MnO_XC. Thus, despite a trend of higher surface area for the MnO_XD, a lower total number of sites was observed, suggesting a coordinational change in the hydroxyl sites. Surface site characterization identified that changes also occurred in the types and densities of surface sites for each hydrologically conditioned Mn oxyhydroxide treatment (pH titration range of 2-10). Drying decreased the total number of sites as well as shifted the remaining sites to more acidic pK_a values. Experimentally determined apparent pH_zpc values decreased with drying, from 6.82 ± 0.06 for the MnO_XW to 3.2 ± 0.3 for the MnO_XD and increased again with rewetting to 5.05 ± 0.05 for the MnO_XC. Higher Ni sorption was observed at pH 5 for all three Mn oxyhydroxide treatments compared to pH 2. However, changes in relative sorptive capacities among the three treatments were observed for pH 2 that are not explainable simply as a function of total binding site density or apparent pH_zpc values. These results are the first to our knowledge, to quantitatively link the changes induced by hydrologic variability for surface acid base characteristics and metal sorption patterns. Further, these results likely extend to other amorphous minerals, such as Fe oxyhydroxides, which are commonly important geochemical solids for metal scavenging in natural environments.