Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH₃COO⁻) or strong (i.e., ) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as “truly” dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., “colloidal” HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).     

Geochemistry of the Rare Earth Elements in Natural Terrestrial Waters：A Review of What Is Currently Knows

The range of observed chemical compositions of natural terrestrial waters varies greatly especially when compared to the essentially constant global composition of the oceans.The concentrations of the REEs in natural terrestrial waters also exhibit more variation than what was reported in seawater,In terrestrial waters ,pH values span the range from acid up to alkaline,In addition,terrestrial waters can range from very dilute waters through to highly concentrated brines.The REE concentrations and their behavior in natural terrestrial waters reflect these compositional ranges,Chemical weathering of rocks represents the source of the REEs to natural terrestrial waters and ,consequently,the REE signature of rocks can impart their REE signature to associated waters,In addition,Because of the typical low solubilities of the REEs both surface and solution complexation can be important in fractionating REEs in aqueous solution.Both of these processes are important in all natural terrestrial waters,however,their relative importance varies as a function of the overall solution composition,In alkaline waters,for example,Solution complexation of the REEs with carbonate ions appears to control their aqueous distributions whereas in acid waters,the REE signature of the labile fraction of the REEs is readily leached from the rocks.In circumneutral pH waters,both processes appear to be important and their relative significance has not yet been determined.     

Organic complexation of rare earth elements in natural waters: Evaluating model calculations from ultrafiltration data

The Stockholm Humic Model (SHM) and Humic Ion-Binding Models V and VI were compared for their ability to predict the role of dissolved organic matter (DOM) in the speciation of rare earth elements (REE) in natural waters. Unlike Models V and VI, SHM is part of a speciation code that also allows us to consider dissolution/precipitation, sorption/desorption and oxidation/reduction reactions. In this context, it is particularly interesting to test the performance of SHM. The REE specific equilibrium constants required by the speciation models were estimated using linear free-energy relationships (LFER) between the first hydrolysis constants and the stability constants for REE complexation with lactic and acetic acid. Three datasets were used for the purpose of comparison: (i) World Average River Water (Dissolved Organic Carbon (DOC) = 5 mg L⁻¹), previously investigated using Model V, was reinvestigated using SHM and Model VI; (ii) two natural organic-rich waters (DOC = 18-24 mg L⁻¹), whose REE speciation has already been determined with both Model V and ultrafiltration studies, were also reinvestigated using SHM and Model VI; finally, (iii) new ultrafiltration experiments were carried out on samples of circumneutral-pH (pH 6.2-7.1), organic-rich (DOC = 7-20 mg L⁻¹) groundwaters from the Kervidy-Naizin and Petit-Hermitage catchments, western France. The results were then compared with speciation predictions provided by Model VI and SHM, successively. When applied to World Average River Water, both Model VI and SHM yield comparable results, confirming the earlier finding that a large fraction of the dissolved REE in rivers occurs as organic complexes This implies that the two models are equally valid for calculating REE speciation in low-DOC waters at circumneutral-pH. The two models also successfully reproduced ultrafiltration results obtained for DOC-rich acidic groundwaters and river waters. By contrast, the two models yielded different results when compared to newly obtained ultrafiltration results for DOC-rich (DOC > 7 mg L⁻¹) groundwaters at circumneutral-pH, with Model VI predictions being closer to the ultrafiltration data than SHM. Sensitivity analysis indicates that the “active DOM parameter” (i.e., the proportion of DOC that can effectively complex with REE) is a key parameter for both Model VI and SHM. However, a survey of ultrafiltration results allows the “active DOM parameter” to be precisely determined for the newly ultrafiltered waters studied here. Thus, the observed discrepancy between SHM predictions and ultrafiltration results cannot be explained by the use of inappropriate “active DOM parameter” values in this model. Save this unexplained discrepancy, the results presented in this study demonstrate that both Model VI and SHM can provide reliable estimates of REE speciation in organic-rich waters. However, it is essential to know the proportion of DOM that can actively complex REE before running these two speciation models.     

溶解态稀土元素在离子吸附型稀土矿区周边地表水中的分布特征及影响因素

选择赣南典型稀土矿区,即寻乌(以轻稀土为代表)、安远(以中稀土为代表)和龙南(以重稀土为代表)为研究区域,于生产期和停产期(停产后半年)分别采集了矿区上游、矿区淋滤废水、矿区山泉水、生活用井水、近矿支流、矿区下游等地表水共90件,分析了溶解态稀土元素在离子吸附型稀土矿区周边地表水中的含量、空间分布特征及影响因素。结果表明:稀土矿的开采对矿区周边地表水中DREE含量影响较大。此外,水粒作用、区域地质背景与风化作用、水化学因素都是影响离子吸附型稀土矿区周边水体DREE行为的主要因素。矿区周边地表水中稀土含量高是我国离子吸附型稀土矿山开采引发的特殊问题。     

Observations on the association between mercury and organic matter dissolved in natural waters

Dissolved mercury in estuarine waters from the Mississippi Delta and Florida Everglades is associated with dissolved organic matter which has the properties of fulvic matter found in soils. Ultrafiltration of water samples demonstrated that mercury and dissolved organic carbon are selectively enriched in the < 500 molecular size cut-off fraction. A decrease in high molecular weight dissolved organic matter with increasing salinity in the Everglades exerts a partial control on the mercury content of these estuarine waters.     

Geochemistry of dissolved rare earth elements in the Equatorial Pacific Ocean

Seawater samples were collected from four locations in the Equatorial Pacific Ocean during the MR02-K06 cruise of the R/V Mirai and analyzed for dissolved rare earth elements (REEs) using inductively coupled plasma mass spectrometry. According to variations of REE concentrations and Yb/La ratios, the results show that the river input of the Papua New Guinea islands may affect the compositions of REEs in the Equatorial Pacific surface water. The Yb/La values and the REE concentrations in the waters deeper than 3,000 m in the western South Pacific and the Equatorial Pacific Oceans, which represent the characteristics of Antarctic Bottom Water (AABW), demonstrate similar variation trend with depth. This result also indicates that the REEs which originated from the South Pacific Ocean have entered the North Pacific Ocean across the equator with AABW intrusion.     

Direct Fourier transform mass spectral analysis of natural waters with low dissolved organic matter

A major obstacle for characterizing dissolved organic matter (DOM) with ultrahigh resolution mass spectrometry has been its low concentrations in natural waters. Many previous mass spectrometric studies of both terrestrial and marine DOM typically have isolated and concentrated the DOM using solid phase C₁₈ extraction disks, ultrafiltration, or XAD resins, all of which are known to discriminate against many different classes of compounds. We have, for the first time, developed an approach to directly analyze natural water samples with less than 6 mg/l DOC (dissolved organic carbon), using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). We demonstrate the sensitivity and ability of sequential selective ion accumulation (SSIA) to detect the thousands of components in a single freshwater DOM sample without any significant pretreatment. By utilizing SSIA, the baseline noise decreases while signal to noise ratios of the peaks increase, allowing for approximately 40% more formulas to be assigned to peaks in the mass spectra.     

Stabilisation of divalent rare earth elements in natural fluorite

Summary ?The occurrence of divalent rare earth elements (Sm²⁺, Yb²⁺, Tm²⁺, and Ho²⁺) in natural fluorite is evaluated using a suite of 37 samples deriving mainly from Sn–W deposits in the Erzgebirge (Germany), Central Kazakhstan, and the Mongolian Altai. Trace element composition was determined by ICP-AES and ICP-MS. The defect structure of the samples was studied by cathodoluminescence (CL), electron paramagnetic resonance (EPR), and optical absorption spectroscopy. Reduction of cubic Sm³⁺, Yb³⁺, Tm³⁺, and Ho³⁺ under radioactive irradiation produces the corresponding divalent centres. Our data suggest a preferable formation of Sm²⁺ and Yb²⁺ under thorium and of Tm²⁺ and Ho²⁺ under uranium irradiation. Irradiation (indicated by intense brownish (thorium) and deep purple (uranium) coloration of fluorite) gives rise to a population of divalent centres in equilibrium with their decay. However, sporadic radioactive irradiation and stabilisation of the divalent state of the REE by other electron defects were found in most cases. Three models of stabilisation of Sm²⁺, Yb²⁺, Tm²⁺, and Ho²⁺ are discussed. The most effective mechanism for Sm, Yb, Tm, and Ho is coupling with Fe³⁺ centres (REE³⁺+Fe²⁺ → REE²⁺+Fe³⁺). Accordingly, the occurrence of Fe³⁺ centres in natural fluorite is regarded to indicate not an oxidising, but rather a reducing environment during fluorite precipitation. Originally incorporated in the divalent form, Fe²⁺ was converted to Fe³⁺ by radioactive irradiation. Such a conclusion is in agreement with the finding of high contents of interstitial fluorine providing tetragonal local compensation of trivalent REE centres in crystals with high Fe³⁺. If Fe is not present, compensation of divalent Sm, Yb, and Tm is achieved by radiogenic oxidation of Ce(Pr, Tb)³⁺ accompanied by charge transfer (REE³⁺+Ce(Pr, Tb)³⁺ → REE²⁺+ Ce(Pr, Tb)⁴⁺). Ho²⁺ is sometimes stabilised by a hole trapped by an electron localised on a F vacancy (Ho³⁺+e⁻ on □_F → REE²⁺+ self-trapped exciton). Because Sm²⁺ is optically active, the stabilisation by Fe³⁺ (stable up to temperatures above 350 °C) or Ce(Pr, Tb)⁴⁺ (unstable even under visible light) in samples may be determined by careful observations in the field. Institut für Geotechnik, ETH Zürich, ETH-H?nggerberg, Zürich, Switzerland Stanford Linear Accelerator Center, Menlo Park, CA, USA Received January 8, 2002; revised version accepted June 10, 2002     

Speciation of adsorbed yttrium and rare earth elements on oxide surfaces

The distribution of yttrium and the rare earth elements (YREE) between natural waters and oxide mineral surfaces depends on adsorption reactions, which in turn depend on the specific way in which YREE are coordinated to mineral surfaces. Recent X-ray studies have established that Y³⁺ is adsorbed to the rutile (1 1 0) surface as a distinctive tetranuclear species. However, the hydrolysis state of the adsorbed cation is not known from experiment. Previous surface complexation models of YREE adsorption have suggested two to four cation hydrolysis states coexisting on oxide surfaces. In the present study, we investigate the applicability of the X-ray results to rare earth elements and to several oxides in addition to rutile using the extended triple-layer surface complexation model. The reaction producing a hydrolyzed tetranuclear surface species

     

Behavior of the rare earth elements in the Oklo natural reactor

A systematic analysis of the abundance and isotopic composition of ten REE (and Ba) in a sample from the reactor zone at the Oklo (Gabon) ore deposit is presented. From this analysis some constraints on the behavior of the REE group during and after the reaction time are determined. Taking into account the complex state of this sample, the main characteristics of the reactor are deduced.From the abundances of isotopes with large neutron capture cross sections the amount of REE (supposed to be natural) added after the reaction time is calculated first. The comparison of the fluence values obtained respectively from the analysis of the Nd and Dy isotopic spectrum indicates a rather good stability of the REE group during the reaction time. The total number (²³⁵U)_f of ²³⁵U nuclei that fissioned during the reaction calculated from different elements of the REE group provides an indication on the relative migration of these elements since the reaction time. Results of these computations suggest a migration of the heavy REE relative to the light REE to outside the reaction zone. As a consequence of these deductions on the behavior of the REE in the Oklo ore, the light REE appear the most appropriate to study the characteristics of the reactor. The reactor characteristics we deduced from this sample (fluence, epithermal index, proportion of nuclides that fissioned, duration of the reactor) are within the range of the ones determined in other studies dealing with REE analysis.     

Speciation of metals in natural waters

The form or speciation of a metal in natural waters can change its kinetic and thermodynamic properties. For example, Cu(II) in the free ionic form is toxic to phytoplankton, while copper complexed to organic ligands is not toxic. The form of a metal in solution can also change its solubility. For example, Fe(II) is soluble in aqueous solutions while Fe(III) is nearly insoluble. Natural organic ligands interactions with Fe(III) can increase the solubility by 20-fold in seawater. Ionic interaction models that can be used to determine the activity and speciation of divalent and trivalent metals in seawater and other natural elements will be discussed. The model is able to consider the interactions of metals with the major (Cl^-, SO₄ ^2-, HCO₃ ^-, CO₃ ^2-, Br^-, F^-) and minor (OH^-, H₂PO₄ ^-, HPO₄ ^2-, PO₄ ^3-, HS^-) anions as a function of temperature (0 to 50 °C), ionic strength [0 to 6 m (m = mol kg-¹)] and pH (1 to 13). Recently, it has been shown that many divalent metals are complexed with organic ligands. Although the composition of these ligands is not known, a number of workers have used voltammetry to determine the concentration of the ligand [L ⁿ ] and the stability constant (K _ML) for the formation of the complex     

Nature and reactions of dissolved organic matter in the interstitial waters of marine sediments

Two organic rich sediments, an oxic muddy sand and a silty mud containing sulphate reducing and methane producing metabolic zones, were sampled from Loch Duich, a fjord type estuary in the N.W. coast of Scotland. Dissolved organic carbon (DOC), as measured by dry combustion and UV absorption, remained constant (8.3–15.8 mg C/l) with depth in the oxic pore waters at a concentration at least twice that of the overlying seawater. DOC in the anoxic pore waters increased linearly with depth from 13.6 at the surface to 55.9–70.5 mg C/l at 80cm. Most of the DOC was present in the high molecular weight (HMW) fraction as separated by ultrafiltration; the low molecular weight (LMW) fraction remained constant (10.0 mg C/l) in both oxic and anoxic pore waters. Spectroscopic data showed the ‘humic’ fraction of the HMW dissolved organic matter was mainly fulvic acid, a small proportion (approx 1%) of humic acid, and a third fraction, possibly melanoidins, which increased relative to fulvic acid with depth. These data confirm the pathway of humification (NissenBaum et al, 1971; nissenbaum and Kaplan, 1972) where HMW organic matter accumulates in pore waters as condensation products of LMW organic substances.     

Direct quantification of rare earth element concentrations in natural waters by ICP-MS

A direct quadrupole ICP-MS technique has been developed for the analysis of the rare earth elements and yttrium in natural waters. The method has been validated by comparison of the results obtained for the river water reference material SLRS-4 with literature values. The detection limit of the technique was investigated by analysis of serial dilutions of SLRS-4 and revealed that single elements can be quantified at single-digit fg/g concentrations. A coherent normalised rare earth pattern was retained at concentrations two orders of magnitude below natural concentrations for SLRS-4, demonstrating the excellent inter-element accuracy and precision of the method. The technique was applied to the analysis of a diluted mid-salinity estuarine sample, which also displayed a coherent normalised rare earth element pattern, yielding the expected distinctive marine characteristics.     

Sedimentary geochemistry of the Yangtze River： Sediment source-to-sink tracing implication

The Yangtze （Changjiang） River as the largest fiver originating from eastern Tibetan Plateau, has increasingly attracted considerable attention of many researchers for almost one hundred years. The fiver linking the Tibetan Plateau with the West Pacific Marginal Sea, encompasses variable source rocks and complicated drainage patterns and spans across distinct climate zones. The increasing human activities in the last 2000 years have significantly changed the weathering process and sediment source-to-sink pattern in the fiver basins. In terms of this, the Yangtze drainage basin as well as the deltaic and coastal areas can be regarded as one of the best regions in the world to investigate the source-to-sink process of continental sediments into the marginal sea. In the past ten years we systematically measured elemental and Sr-Nd-Pb isotopic compositions of the Yangtze riverine sediments which were collected from the mainstream and main tributaries. Analytical results clearly showed that the Yangtze sediments yield geochemical compositions different from those of other fiver sediments due to the very complicated source rock types and variable chemical weathering regimes in the large drainage basin. REE and Sr-Nd isotopic compositions suggest that the sediment source-to-sink pattern in the modern Yantze River basins varies considerably from the upper basin to the lower valley. Different chemical compositions among the main tributaries and the mainstream are responsible for the compositional variations of the Yangtze River sediments. It is a piece of quite challenging work to establish a sediment source-to-sink model to quantifying the contributions of the main tributaries to the mainstream.     

Water–granite interaction: Clues from strontium,neodymium and rare earth elements in soil and waters

Strontium-, Nd-, and rare-earth-element-isotope data are presented from rock, weathered rock (arene) and saprolite, sediment and soil, shallow and deep groundwater (e.g. mineral-water springs), and surface waters in the Margeride massif, located in the French Massif Central. Granitoid rock and gneiss are the main lithologies encountered in the Margeride, which corresponds to a large and 5-km-deep laccolith. Compared to bedrock, the Sr isotopes in arene, regolith, sediment and soil strongly diverge with a linear increase in the ⁸⁷Sr/⁸⁶Sr and Rb/Sr ratios. Neodymium isotopes fluctuate least between bedrock and the weathering products. In order to characterise the theoretical Sr isotopic signature IRf(Sr) of water interacting with granite, a dissolution model was applied, based on the hypothesis that most of the Sr comes from the dissolution of plagioclase, K-feldspar and biotite. Similar to the Sr model, an approach was developed for modelling the theoretical Nd isotopic signature IRf(Nd) of water interacting with a granite, assuming that most Nd originates from dissolution of the same minerals as those that yield Sr, plus apatite. The IRf(Sr) ratio of water after equilibration with the Sr derived from minerals was calculated for the Margeride granite and compared to values measured in surface- and groundwaters. Comparison of the results shows agreement between the calculated IRf(Sr) and the observed ⁸⁷Sr/⁸⁶Sr ratios. When calculating the IRf(Nd) ratio of water after equilibration with the Nd derived from minerals of the Margeride granite, the results indicated good agreement with surface-water values, whereas mineralised waters analysed within the Margeride hydrosystem could not be directly linked to weathering of the granite alone. Because the recharge area of deep groundwater is located on the Margeride massif, very deep circulation involving interaction with other rocks (e.g. shales) at depths of >5 km must be considered.     

Adsorption of natural dissolved organic matter at the oxide/water interface

Natural organic matter is readily adsorbed by alumina and kaolinite in the pH range of natural waters. Adsorption occurs by complex formation between surface hydroxyls and the acidic functional groups of the organic matter. Oxides with relatively acidic surface hydroxyls, e.g. silica, do not react strongly with the organic matter. Under conditions typical for natural waters, almost complete surface coverage by adsorbed organic matter may be expected for alumina, hydrous iron oxides and the edge sites of aluminosilicates. Potentiometric titration and electrophoresis indicate that most of the acidic functional groups of the adsorbed organic matter are neutralized by protons from solution. The organic coating is expected to have a great influence on subsequent adsorption of inorganic cations and anions.     

The behaviour of the rare earth elements during mixing of river and sea waters

Rare earth element concentrations have been measured in organic-rich Luce river water and coastal sea water. Concentrations (e.g. ～350?1850 pmol/kg Nd in the Water of Luce and ～45?350 pmol/ kg Nd in Luce Bay) are related to the presence of particles, with 30–60% of the REE associated with >0.4?0.7 μm particles, and to riverine Fe concentrations. REE fractionation occurs in the river water the submicrometre river water is heavy REE enriched whereas the coarser fraction has a more shale-like REE pattern.Laboratory experiments show that the REE in organic-rich river waters are chiefly associated with Feorganic matter colloids which flocculate during estuarine mixing. Preferential removal of heavy REE (～95%) relative to light REE (～60%) occurs, but no Ce anomaly is developed. In contrast, no REE removal occurs during estuarine mixing with organic-poor river water.     

Abiotic interactions of natural dissolved organic matter and carbonate aquifer rock

Abiotic interactions between natural dissolved organic matter (NDOM) and carbonate aquifer rock may be controlling factors of biogeochemical processes and contaminant fate in carbonate aquifer systems. The importance and effects of these interactions were examined using batch adsorption experiments of soil NDOM and representative carbonate sorbents from the Floridan Aquifer. Adsorption of NDOM carbon to aquifer rocks was well-described using a modified linear model and was mostly reversible. Significant adsorption was observed at higher NDOM concentrations, while the release of indigenous organic matter from the rocks occurred at lower concentrations. Longer interaction periods led to more adsorption, indicating that adsorption equilibrium was not achieved. For relatively pure carbonate rock samples, sorbent surface area was found to be the most important controlling factor of adsorption, whereas the presence of indigenous organic matter and subdominant mineral phases were more important, when they occurred. Preferential adsorption of a high over low molecular weight and humic over fulvic components of NDOM onto carbonate sorbents was detected using liquid size exclusion chromatography and excitation–emission fluorometry, respectively. The presence of NDOM inhibited mineral dissolution, though this inhibition was not proportional to NDOM concentration as surface area and mineralogy of carbonate sorbents played additional roles. Though the NDOM–carbonate rock adsorption mechanism could not be completely determined due to the heterogeneity and complexity of NDOM and sorbent surfaces, it is speculated that both rapid and weak outer-sphere bonding and stronger but slower hydrophobic interaction occur. These results have important implications for groundwater quality and hydrogeologic projects such as aquifer storage and recovery.