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).     

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.     

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

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

Importance of heavy metal-organic matter interactions in natural waters

The role of organic ligands in metal complexing in natural waters has received little attention because of uncertainties regarding both the abundance and nature of dissolved organic carbon compounds. Recent data show that the bulk of dissolved organic matter in natural waters consists of highly oxidized and chemically and biologically stable polymeric compounds closely resembling soil humic substances. Average molar concentrations of these aquatic humics in major U.S. rivers range from 5 × 10^?6to 3 × 10^?5 moles 1^?1. Fractional elution of soil organic matter by meteoric waters may be considered to be the main process contributing to the presence of humic matter in rivers. The aquatic humic polymers participate in complex formation through ionizable functional groups with a range of differential acidities. The stabilities of metal-humic complexes in natural waters are higher than those of the corresponding inorganic metal complexes. Quantitative evaluation of the metal-organic interactions can be approached by applying variable equilibrium functions which take into account the differential physico-chemical characteristics of the active complexing sites on the polymer molecule. Assuming an average humic concentration of 10 mg 1^?1, complexation of trace metals can be significant even in the presence of excess concentrations of major cations.     

Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.     

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.     

The solubility control of rare earth elements in natural terrestrial waters and the significance of PO 4 3− and CO 3 2− in limiting dissolved rare earth concentrations: A review of recent information

Rare earth element (REE) concentrations in alkaline lakes, circumneutral pH groundwaters, and an acidic freshwater lake were determined along with the free carbonate, free phosphate, and free sulfate ion concentrations. These parameters were used to evaluate the saturation state of these waters with respect to REE phosphate and carbonate precipitates. Our activity product estimates indicate that the alkaline lake waters and groundwaters are approximately saturated with respect to the REE phosphate precipitates but are significantly undersaturated with respect to REE carbonate and sulfate precipitates. On the other hand, the acidic lake waters are undersaturated with respect to REE sulfate, carbonate, and phosphate precipitates. Although carbonate complexes tend to dominate the speciation of the REEs in neutral and alkaline waters, our results indicate that REE phosphate precipitates are also important in controlling REE behavior. More specifically, elevated carbonate ion concentrations in neutral to alkaline natural waters tend to enhance dissolved REE concentrations through the formation of stable REE-carbonate complexes whereas phosphate ions tend to lead to the removal of the REEs from solution in these waters by the formation of REE-phosphate salts. Removal of REEs by precipitation as phosphate phases in the acid lake (pH=3.6) is inconsequential, however, due to extremely low [PO ₄ ^3– ] _F concentrations (i.e., 10^–23 mol/kg).     

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.     

Rare earth elements in pore waters of marine sediments

The rare earth elements (REEs) were measured in pore waters of the upper ∼25 cm of sediment from one site off Peru and three sites on the California margin. The pore water REE concentrations are higher than sea water and show systematic down core variations in both concentration and normalized pattern. From these analyses and from comparison to other chemical species measured (dissolved Fe, Mn, Ba, oxygen, nitrate, phosphate), it is suggested that pore water REEs can be grouped into three categories: those that are from an Fe-source, those that are from a POC-source, and cerium oxide. REEs from the Fe-source appear where anoxia is reached; they have a distinctive “middle-REE (MREE) enriched” pattern. The concentrations in this source are so elevated that they dominate REE trends in the Fe-oxide reduction zone. The net result of flux from the POC-source is relative enrichment of heavy-REEs (HREEs) over light-REEs (LREEs), reflecting remineralizing POC and complexation with DOC. A common “linear” REE pattern, seen in both oxic and anoxic sediments, is associated with this POC-source, as well as a “HREE enriched” pattern that is seen in surficial sediments at the Peru site. Overall, the pore water results indicate that Mn-oxides are not an important carrier of REEs in the oceans.A REE biogeochemical model is presented which attempts to reconcile REE behavior in the water and sediment columns of the oceans. The model proposes that POC, Fe-oxide and Ce-oxide sources can explain the REE concentration profiles and relative abundance patterns in environments ranging from oxic sea water to anoxic pore water. The model is also consistent with our observation that the “Ce-anomaly” of pore water does not exceed unity under any redox condition.     

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.     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation

Published experimental data for Al(III) and Fe(III) binding by fulvic and humic acids can be explained approximately by the Humic Ion-Binding Model VI. The model is based on conventional equilibrium reactions involving protons, metal aquo ions and their first hydrolysis products, and binding sites ranging from abundant ones of low affinity, to rare ones of high affinity, common to all metals. The model can also account for laboratory competition data involving Al(III), Fe(III) and trace elements, supporting the assumption of common binding sites. Field speciation data (116 examples) for Al in acid-to-neutral waters can be accounted for, assuming that 60-70 % (depending upon competition by iron, and the chosen fulvic acid : humic acid ratio) of the dissolved organic carbon (DOC) is due to humic substances, the rest being considered inert with respect to ion binding. After adjustment of the model parameter characterizing binding affinity within acceptable limits, and with the assumption of equilibrium with a relatively soluble form of Fe(OH)₃, the model can simulate the results of studies of two freshwater samples, in which concentrations of organically complexed Fe were estimated by kinetic analysis.The model was used to examine the pH dependence of Al and Fe binding by dissolved organic matter (DOM) in freshwaters, by simulating the titration with Ca(OH)₂ of an initially acid solution, in equilibrium with solid-phase Al(OH)₃ and Fe(OH)₃. For the conditions considered, Al, which is present at higher free concentrations than Fe(III), competes significantly for the binding of Fe(III), whereas Fe(III) has little effect on Al binding. The principal form of Al simulated to be bound at low pH is Al³⁺, AlOH²⁺ being dominant at pH >6; the principal bound form of Fe(III) is FeOH²⁺ at all pH values in the range 4-9. Simulations suggest that, in freshwaters, both Al and Fe(III) compete significantly with trace metals (Cu, Zn) for binding by natural organic matter over a wide pH range (4-9). The competition effects are especially strong for a high-affinity trace metal such as Cu, present at low total concentrations (∼1 nM). As a result of these competition effects, high-affinity sites in humic matter may be less important for trace metal binding in the field than they are in laboratory systems involving humic matter that has been treated to remove associated metals.     

Sediment-water interactions of thallium under simulated estuarine conditions

Thallium(I) has been added to estuarine sediment suspended in various natural and artificial aqueous samples in order to examine its reactivity under simulated estuarine conditions. In river water and sea water, adsorption of Tl to sediment was so rapid that a period of desorption-relaxation succeeded instantaneous adsorption. Entire time-courses could not be fitted with a conventional kinetic model, but pseudo-first-order forward and reverse rate constants of 0.0044 and 0.30 h⁻¹, respectively, were derived for river water by omitting measurements defining the adsorption “overshoot” observed at the onset of the experiment. The extent of adsorption after a 16 h equilibration period was considerably greater in river water than in sea water, and displayed a quasi-linear increase with increasing pH over the range 2-9 in the former but no clear dependence on pH in the latter. A logarithmic reduction in the sediment-water distribution coefficient, K_D, was observed on estuarine mixing from river water to sea water. Experiments conducted in electrolyte solutions coupled with inorganic equilibrium speciation modeling revealed that the effect was the combined result of a reduction in the activity of Tl⁺, an increase in the proportion of TlCl⁰ and increasing competition for adsorption sites from K⁺ with an increase in salinity. Overall, there was little experimental evidence for either the oxidation of Tl⁺ or its complexation by dissolved organic matter. The findings of the investigation are discussed in terms of the likely behavior of Tl in estuaries.     

Chemical weathering in the drainage basin of a tropical watershed (Nsimi-Zoetele site, Cameroon) : comparison between organic-poor and organic-rich waters

This study deals with the weathering processes operating at the scale of a small catchment (Nsimi-Zoetele, Cameroon) and is focused on the role of organic colloids on mineral weathering and transport of elements in natural waters. Samples of river, spring and groundwaters from Nsimi-Zoetele were filtered through membranes of decreasing pore size (0.22 μm, 0.025 μm, or: 300,000 Da, 5000 Da) to separate colloidal fractions from the truly dissolved one. Major and trace elements and dissolved organic carbon (DOC) were analysed in each fraction. Two kinds of waters can be distinguished in the catchment: clear and coloured waters. Clear waters exhibit low concentrations of major and trace elements and DOC. Elements are carried in these solutions in a true dissolved form except Al and rare earth elements (REEs). By contrast, the higher abundances of Al, Fe and trace elements in coloured waters are controlled by the colloidal fraction. Thermodynamic equilibrium calculations show that clear waters are in equilibrium with kaolinite and iron oxi-hydroxide which are major minerals in the weathered soil. For coloured waters, the aqueous speciation of Ca, Mg, Cu, Fe, Al, La and Th was calculated taking into account the complexes with humic acids. Speciation calculations for Cu, Fe, Al, La, Th show a strong complexation with humic acids, in good agreement with the results of the filtration experiments. By contrast, although filtration experiments show a strong control of major cations by organic matter (for example 75% for Ca), speciation calculations reveal that their complexes with humic ligands do not exceed a few percent of total dissolved elements. This discrepancy is explained as an artefact induced by the organic colloids and occurring during the filtration procedure. Finally, both filtration experiments and speciation calculations show that organic matter plays an important role in natural DOC-rich waters. Organic acids increase significantly the dissolution rates of silicates and oxi-hydroxides and thus the amounts of solutes and of complexed elements leaving the catchment.     

Comparison of the behaviour of rare earth elements in surface waters,overburden groundwaters and bedrock groundwaters in two granitoidic settings,Eastern Sweden

This work, which was done within the Swedish nuclear waste management program, was carried out in order to increase the understanding of the mobility and fate of rare earth elements (REEs) in natural boreal waters in granitoidic terrain. Two areas were studied, Forsmark and Simpevarp, one of which will be selected as a site for spent nuclear fuel. The highest REE concentrations were found in the overburden groundwaters, in Simpevarp in particular (median ∑REE 52 μg/L), but also in Forsmark (median ∑REE 6.7 μg/L). The fractionation patterns in these waters were characterised by light REE (LREE) enrichment and negative Ce and Eu anomalies. In contrast, the surface waters had relatively low REE concentrations. They were characterised either by an increase in relative concentrations throughout the lanthanide series (Forsmark which has a carbonate-rich till) or flat patterns (Simpevarp with carbonate-poor till), and had negative Ce and Eu anomalies. In the bedrock groundwaters, the concentrations and fractionation patterns of REEs were entirely different from those in the overburden groundwaters. The median La concentrations were low (just above 0.1 μg/L in both areas), only in a few samples were the concentrations of several REEs (and in a couple of rare cases all REEs) above the detection limit, and there was an increase in the relative concentrations throughout the lanthanide series. In contrast to these large spatial variations, the temporal trends were characterised by small (or non existent) variations in REE-fractionation patterns but rather large variations in concentrations. The Visual MINTEQ speciation calculations predicted that all REEs in all waters were closely associated with dissolved organic matter, and not with carbonate. In the hydrochemical data for the overburden groundwater in particular, there was however a strong indication of association with inorganic colloids, which were not included in the speciation model. Overall the results showed that within a typical boreal granitoidic setting, overburden groundwaters are enriched in REEs, organic complexes are much more important than carbonate complexes, there is little evidence of significant mixing of REEs between different water types (surface, overburden, bedrock) and spatial variations are more extensive than temporal ones.     

Reduced sulfur species in a stratified seawater lake (Rogoznica Lake, Croatia); seasonal variations and argument for organic carriers of reactive sulfur

Over a period of a year, Hg⁰-reactive, total reduced sulfur species (RSS_T), as well as a non-volatile fraction that cannot be gas-stripped at pH ∼2 (RSS_NV), have been measured by voltammetry in a stratified, saline lake. In the hypolimnion, RSS_T is dominated by unusually high (up to 5 mM) dissolved divalent sulfur (S^−II), present as H₂S + HS⁻ and as inorganic polysulfides (H_xS_n^x−2). Less abundant RSS_NV is attributed to dissolved zero-valent sulfur (S⁰) in inorganic polysulfides. Assuming negligible contribution of organic S⁰ species in the hypolimnion, the equilibrium distribution of polysulfide ions is calculated; S₅²⁻ is found to predominate. In the epilimnion, all RSS_T consists of RSS_NV within analytical uncertainty. Through spring and summer, RSS_T and RSS_NV display little vertical or seasonal variation, but they increase dramatically when stratification breaks down in autumn. Based on decay rate, RSS during mixing events is attributed to dissolved S₈ from oxidation of sulfide and decomposition of inorganic polysulfides. This hypothesis quantitatively predicts precipitation of elemental sulfur in a year when colloidal sulfur was observed and predicts no precipitation in a year when it was not observed. Except during mixing events, the entire water column is undersaturated with respect to both rhombic sulfur and biologic sulfur, and the limited variations of RSS exclude hydrophobic and volatile aqueous S₈ as a major species. During such periods, RSS (typically 8 nM) may be associated with organic carbon, perhaps as adsorbed S₈ or as covalently bound polysulfanes or polysulfides. The hypolimnion is viewed as a zero-valent sulfur reactor that creates S⁰-containing, dissolved organic macromolecules during stable stratification periods. Some are sufficiently degradation-resistant and hydrophilic to be dispersed throughout the lake during mixing events, subsequently giving rise to ∼10⁻⁸ M RSS in the oxic water column. Voltammetrically determined RSS in oxic natural waters has often been described as “sulfide” or “metal complexed sulfide”, implying an oxidation state of S^−II; we argue that RSS in oxic Rogoznica Lake waters is mainly S⁰.     

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.     

Cycling of dissolved elemental mercury in Arctic Alaskan lakes

Aqueous production and water-air exchange of elemental mercury (Hg⁰) are important features of the environmental cycling of Hg. We investigated Hg⁰ cycling in ten Arctic Alaskan lakes that spanned a wide range in physicochemical characteristics. Dissolved gaseous Hg (DGM, dominated by Hg⁰) varied from 40 to 430 fM and averaged 200 fM. All surface waters were supersaturated relative to the atmosphere. DGM averaged 3 ± 2% of dissolved (i.e., filter passing) dissolved total mercury (DTM) and 15 ± 6% of dissolved labile Hg (DLM). In-lake DGM profiles generally followed the vertical distribution of light, indicating photoreduction of Hg(II) complexes as a source of Hg⁰. Additionally, DGM correlated linearly with DLM (r² = 0.82, p < 0.0001) in the lake surface, signifying that Hg complexes (mostly organic Hg associations) in dissolved phase are photoreducible and contribute to production of DGM. Further, a positive relation between DGM/DTM and both K_a (light attenuation coefficient; r² = 0.73, p < 0.02) and DOC (r² = 0.60, p = 0.02) suggests that solar radiation and dissolved organic matter control DGM production and its cycling. An average rate of DGM formation (0.6 ± 0.2% of DTM d⁻¹; range, 0.20.8) was estimated by assuming steady state with the evasional rate. In-lake DGM formation occurs at lower rates in waters with greater suspended particulate matter and dissolved organic carbon (DOC), pointing to the significant role of organic matter plays in controlling DGM formation in these aquatic systems. Estimated evasional fluxes of Hg⁰ (average, 140 ± 50 pmol m⁻² d⁻¹; range, 60-200) were comparable to those of temperate lakes (e.g., Wisconsin, Michigan). In arctic lakes, the rate of evasion during ice-free periods (7 ± 3 nmol m⁻² yr⁻¹) is similar to the atmospheric input of Hg (wet + dry) to the lakes based on levels in summertime precipitation but not including additional sources, e.g., springtime depletion.     

The radiocarbon age of organic carbon in marine surface sediments

Long-term carbon cycling and climate change are strongly dependent on organic carbon (OC) burial in marine sediments. Radiocarbon (¹⁴C) has been widely used to constrain the sources, sinks, and processing of sedimentary OC. To elucidate the dominant controls on the radiocarbon content of total organic carbon (¹⁴C_TOC) accumulating in surface sediments we construct a box model that predicts ¹⁴C_TOC in the sediment mixed layer (measured as fraction modern, Fm). Our model defines three distinct OC pools (“degradable,” “semi-labile,” and “refractory”) and assumes that ¹⁴C_TOC flux to sediments is exclusively derived from surface ocean primary productivity, and hence follows a “generic” surface ocean dissolved inorganic carbon (DIC) bomb curve. Model predictions are compared to a set of 75 surface sediment samples, which span a wide geographic range and reflect diverse water column and depositional conditions, and for which sedimentation rate and mixed-layer depth are well characterized. Our model overestimates the Fm value for a majority (65%) of these sites, especially at shallow water depths and for sites characterized by depleted δ¹³C_TOC values. The model is most sensitive to sedimentation rate and mixed-layer depth. Therefore, slight changes to these parameters can lead to a match between modeled and measured Fm values at many sites. Yet, in some cases, we find that measured Fm values cannot be simulated without large and unrealistic changes to sedimentation rate and mixed-layer depth. These results point to sources of pre-aged OC to surface sediments and implicate soil-derived terrestrial OC, reworked marine OC, and/or anthropogenic carbon as important components of the organic matter present in surface sediments. This approach provides a valuable framework within which to explore controls on sedimentary organic matter composition and carbon burial over a range of spatial and temporal scales.     

Submarine groundwater discharge is an important net source of light and middle REEs to coastal waters of the Indian River Lagoon, Florida, USA

Porewater (i.e., groundwater) samples were collected from multi-level piezometers across the freshwater-saltwater seepage face within the Indian River Lagoon subterranean estuary along Florida’s (USA) Atlantic coast for analysis of the rare earth elements (REE). Surface water samples for REE analysis were also collected from the water column of the Indian River Lagoon as well as two local rivers (Eau Gallie River, Crane Creek) that flow into the lagoon within the study area. Concentrations of REEs in porewaters from the subterranean estuary are 10-100 times higher than typical seawater values (e.g., Nd ranges from 217 to 2409 pmol kg⁻¹), with submarine groundwater discharge (SGD) at the freshwater-saltwater seepage face exhibiting the highest REE concentrations. The elevated REE concentrations for SGD at the seepage face are too high to be the result of simple, binary mixing between a seawater end-member and local terrestrial SGD. Instead, the high REE concentrations indicate that geochemical reactions occurring within the subterranean estuary contribute substantially to the REE cycle. A simple mass balance model is used to investigate the cycling of REEs in the Indian River Lagoon and its underlying subterranean estuary. Mass balance modeling reveals that the Indian River Lagoon is approximately at steady-state with respect to the REE fluxes into and out of the lagoon. However, the subterranean estuary is not at steady-state with respect to the REE fluxes. Specifically, the model suggests that the SGD Nd flux, for example, exported from the subterranean estuary to the overlying lagoon waters exceeds the combined input to the subterranean estuary from terrestrial SGD and recirculating marine SGD by, on average, ∼100 mmol day⁻¹. The mass balance model also reveals that the subterranean estuary is a net source of light REEs (LREE) and middle REEs (MREE) to the overlying lagoon waters, but acts as a sink for the heavy REEs (HREE). Geochemical modeling and statistical analysis further suggests that this fractionation occurs, in part, due to the coupling between REE cycling and iron redox cycling within the Indian River Lagoon subterranean estuary. The net SGD flux of Nd to the Indian River Lagoon is ∼7-fold larger than the local effective river flux to these coastal waters. This previously unrecognized source of Nd to the coastal ocean could conceivably be important to the global oceanic Nd budget, and help to resolve the oceanic “Nd paradox” by accounting for a substantial fraction of the hypothesized missing Nd flux to the ocean.