Gorleben Groundwater Research Articles

The lanthanum precipitation method. Part 2: Quantification of the conditional interaction constant between technetium(IV) and humic substances

The interaction between colloidal Tc(IV) species and colloidal Gorleben humic substances (HS) was quantified after application of the La-precipitation method on supernatant solutions obtained under various experimental conditions but at constant ionic strength of the Gorleben groundwater (0.04 M). The determined interaction constant Log K HS (2.3 ± 0.3) remained unchanged over a large range of Tc(IV) and HS concentrations and was independent of the pH of the original supernatant solution (pH range 6–10), Tc(IV)–HS loading (10 −3–10 −6 mol Tc g −1 HS) and the nature of the reducing surface (Magnetite, Pyrite and Gorleben sand) used for the pertechnetate reduction. The Log K HS value determined by the La-precipitation method is lower than the Log K value obtained from a previous study where the interaction between colloidal Tc(IV) species and Gorleben humic substances was quantified using a modified Schubert approach (2.6 ± 0.3). The La-precipitation method allows to accurately determine the amount of Tc(IV) associated with HS but leads to a (small) overestimation of the free inorganic Tc(IV) species.

Prognosticating the humic complexation for redox sensitive actinides through analogy, using the charge neutralisation model

AbstractThe complexation of redox sensitive elements by humic acid (HA), described through the charge neutralisation model (CNM), has been reviewed in order to have a comprehensive scope. The data acquired in HUMICS program on thorium(IV), and data available in the literature, were reinterpreted according to the CNM, and adapted to uranium(IV), neptunium(IV) and plutonium(IV) through analogy in order to draw a boundary prediction. Otherwise, available data obtained in the framework of the CNM were used, or adapted if necessary, for other redox states when the analogy is justified,i.e.Am3+-Cm3+for Pu3+, NpO2+for PuO2+and UO22+for PuO22+.The obtained speciation diagrams indicate that, when (HA)=100 mg/L, redox sensitive actinides should be reduced to their +IV state whenEh≤650 mV/SHE for plutonium,Eh≤100 mV/SHE for neptunium andEh≤-20 mV/SHE for U. Plutonium could be present as mixtures of plutonium(III) and (IV) depending on the pH value in reducing ground waters -150 ≤Eh(mV/SHE) ≤ 150. The known reduction of neptunium(V) to neptunium(IV) in Gorleben ground waters seems also well represented, so is the stability of uranium(VI) in humic solution whenEh≥ 100 mV/SHE. Conversely, the known association of plutonium(VI) in marine systems is not satisfactorily represented, so does is the uranium behaviour under reducing conditions. Experiments under well-controlled conditions are still needed to ascertain the plutonium and uranium comportment in the presence of humic acid.

Evidence for the interaction of technetium colloids with humic substances by X-ray absorption spectroscopy.

Spectroscopic extended X-ray absorption fine structure (EXAFS) evidence was obtained on the chemical environment of 99Tc(IV) atoms formed upon introduction of TcO4- into four types of laboratory-scale synthetic and natural systems which mimic in situ natural reducing conditions in humic-rich geochemical environments: (a) magnetite/pyrite in synthetic groundwater in the absence of humic substances (HSs), (b) magnetite/pyrite in natural Gorleben groundwater in the presence of HSs, (c) Boom clay sediment mixed with synthetic groundwater, and (d) Gorleben sand mixed with natural Gorleben groundwater. The investigated systems obey to pH 8-9 conditions, and all measured samples show similar EXAFS spectra for Tc, which could be fitted by a hydrated TcO2 x xH2O phase. The results are interpreted as follows: upon introduction of high concentrations (millimolar to micromolar) of TcO4-to chemically reducing environments, small Tc(IV) oxidic polymers are formed, which either may aggregate into larger units (colloids) and finally precipitate or may interact in their polymeric form with (dissolved and immobile) humic substances. This latter type of interaction--Tc(IV) colloid sorption onto HSs--differs significantly from the generally accepted metal--humate complexation and therefore offers new views on the possible reaction pathways of metals and radionuclides in humic-rich environments.

Functional group analysis of natural organic colloids and clay association kinetics using C(1s) spectromicroscopy

The quantification of natural humic colloid functional group content and chemical association of humic substances with clay minerals exerts a crucial role in the colloid-borne mobility of actinides due to the functional group dependent strong interaction with multivalent metal ions. Functional group quantification in isolated fulvic acids of the Gorleben groundwater (Lower Saxony, NW Germany) by comparison of high resolution C(ls) NEXAFS spectra deconvolution with 3 C-NMR measurements showed good correlation (r 2 > 0.9) and gives a potential quantification tool in complex natural groundwater systems. Time resolved soft X-ray spectromicroscopy on dissolved organic carbon stabilized SWy-2 smectite colloids revealed an enrichment of carboxyl groups on broken edges (silanol/aluminol groups) at short contact times (Ih). With longer contact times (7d, 6 months) the clay associated organic carbon increases and significantly higher aromatic content associated with basal surfaces were detected. The enhanced sorption of aromatic compounds can be related to an increase in mineral surface hydrophobicity and/or preferential sorption on charged siloxane surfaces.

Evidence for the existence of Tc(IV) – humic substance species by X-ray absorption near-edge spectroscopy

SummaryThe redox–sensitive fission product technetium–99 has been investigated in systems containing different reducing solid phases (pyrite, magnetite, ironsulphide and Gorleben sand) on the one hand and Gorleben groundwater, which contains a high amount of humic substances, on the other hand. Initially, technetium–99 was added to these systems as pertechnetate (Tc(VII)), which was reduced in presence and absence of humic substances with the aid of the different reducing surfaces (neutral to alkaline pH). Both in absence and presence of humic substances, Tc concentrations were observed which exceeded the TcO2solubility limit, whereby the presence of humic substances had a 100 fold higher Tc concentration compared to its absence. Using the La–precipitation method, it was shown that Tc(IV) inorganic colloids and organic colloids were quantitatively precipitated. It was demonstrated for the first time by a combination of chemical speciation methods (La–precipitation method and gel permeation chromatography) and XANES spectroscopy of the humic substance containing supernatant solutions, that Tc(IV) species were formed in these systems, indicating an association between Tc(IV) and humic substances.

Characterization of Gorleben groundwater colloids by atomic force microscopy.

Groundwater colloids from the Gorleben site (Lower Saxony, Germany) are characterized in the presence of Eu(III) by tapping-mode atomic force microscopy (AFM) with phase contrast imaging. Using a liquid cell the method allows investigations of samples being in contact with aqueous solution. This ensures that complex structures are kept in their native hydrated state. Different types of colloids and aggregates are found by AFM, e.g., spherical particles, fibrous structures, and structures which appear to be hollow. A partial coating of the edges of clay particles with humic colloids can be assumed from phase contrast images. Therefore, aquatic colloids and their aggregates found in Gorleben groundwater can be characterized as a complex mixture of components, which may influence the migration of groundwater contaminants in different processes.

Humic colloid-borne natural polyvalent metal ions: dissociation experiment.

The natural association nature of the humic colloid-borne trace elements is investigated. Rare earth elements (REE) Th and U are chosen as naturally occurring representatives and chemical homologues for actinides of different oxidation states present in nuclear waste. Tri- and tetravalent elements in two investigated Gorleben groundwaters (Gohy-532 and -2227) almost exclusively occur as humic or fulvic colloid-borne species. Their desorption behavior from colloids is examined in the unperturbed groundwater (pH approximately 8) under anaerobic conditions (Ar/1% CO2) by addition of a chelating cation exchanger resin. Particularly, the dissociation process of naturally occurring Eu(III) in the groundwater is compared with the Eu(III) desorption from its humate complex prepared with purified Aldrich humic acid in a buffered aqueous solution at pH approximately 8. The Eu(III) dissociation from the groundwater colloids is found to be considerably slower than found for the humate complex synthesized in the laboratory. This suggests that under natural aquatic conditions the Eu(III) binding in colloids is chemically different from the simple humate complexation as observed in the laboratory experiment. The colloid characterization bythe size exclusion chromatography (SEC) and the flow field-flow fractionation (FFFF) indicates that natural colloid-borne trace elements are found predominantly in colloids of larger size (>15 nm in size), while Eu(III) in its humate complex is found mainly in colloids of hydrodynamic diameters <5 nm. The slower desorption kinetics and the larger colloid size suggest that the polyvalent metal ion binding in natural humic colloids is associated to polynucleation with other co-present trace metal ions. Radiotracer experiments reveal that isotopic equilibria with the naturally colloid-borne trace elements are not attained within a period of more than 100 days, indicating irreversible binding of at least a part of colloid-borne polyvalent trace elements. The different kinetic properties of colloid-bound Eu(III) are discussed taking the aqueous speciation based on thermodynamic data into account.

Numerical modeling of humic colloid borne Americium (III) migration in column experiments using the transport/speciation code K1D and the KICAM model

The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parameters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.

Speciation of Uranium in Gorleben Groundwaters

Speciation of Uranium in Gorleben Groundwaters

Complexation of the Uranyl Ion with Aquatic Humic Acid

The complexation of the uranyl(VI) ion with aquatic humic acid from Gorleben groundwater (Gohy-573) is studied in 0.1 M NaClO[sub 4] at pH 4 under argon atmosphere. The concentration range investigated is from 1 x 10[sup -7] to 1 x 10[sup -5] mol/l for the uranyl ion and from 1 x 10[sup -6] to 1.12 x 10[sup -5] mol/l for the humic acid. Three different experimental methods are applied to separate the uncomplexed uranyl ion from the uranyl humate complex, using differences of the two species in size by ultrafiltration at the pore size of about 1 nm, in charge by anion exchange separation and in spectroscopic properties by time resolved laser fluorescence spectroscopy (TRLFS). No reduction of U(VI) to U(IV) is observed in the course of the humate complexation process. The experimental results confirm that the prevailing complexation reaction is charge neutralization of the UO[sup 2+][sub 2] ion with two proton exchanging sites of humic acid. At pH 4 in 0.1 M NaClO[sub 4], where the hydrolysis of the uranyl ion appears negligible, the fraction of proton exchanging sites of the humic acid that can be occupied by the uranyl ion (called the loading capacity (LC) of the uranyl ion) is determined to be 0.185[+-]0.003. The complexation constant evaluated by taking the loading capacity into account is found to be log[beta] = 6.16[+-]0.13, which is a grand average of all values determined by the three experimental procedures under consideration. This value is valid for the humate complexation of the non-hydrolyzed uranyl ion, being independent of pH and ionic strength. (orig.)

Characterization of humic and fulvic acids from Gorleben groundwater

The humic material extracted from one of the Gorleben groundwaters is separated into humic and fulvic acids, and characterized, together with a commercial humic acid from Aldrich Co., for their chemical composition, size distribution, proton exchange capacity and spectroscopic characteristics. The results are compared with one another and with the literature data of other humic acids. The humic acid is fractionated by gel permeation chromatography into different size groups and the fractions are subjected to IR and 1H-NMR spectroscopy. The high molecular weight fractions (>70000 Dalton) are poor in carboxylic groups, whereas the major fractions (approx. 10000 Dalton) contain organic acids of large molecular entities.

Speciation of Transuranic Ions in Groundwater by Laser-Induced Photoacoustic Spectroscopy (LPAS)

ABSTRACTThe speciation of the Am(III) ion in various chemical states is illustrated using laser-induced photoacoustic spectroscopy (LPAS). Based on these reference LPAS spectra, the actual chemical states of Am(III) in one of Gorleben groundwaters are systematically verified. The a-radiolytic oxidation of Am(III) to Am(V) in the concentrated NaCl solution and their carbonate complexation are also speciated for the purpose of demonstration.

Humic Colloid Generation of Transuranic Elements in Groundwater and Their Migration Behaviour

AbstractThe generation of humic colloids of Am(III) has been investigated in Gorleben groundwaters containing different amounts of humic substances. Dissolved organic carbon (DOC) in these groundwaters consists mainly of humic acid and fulvic acid, which is present in a colloidal form through aggregation with trace heavy metal ions of groundwater constituents. Concentrations of these heavy metal ions are proportional to the DOC concentration. The generation of Am(III) pseudocolloids through geochemical interactions with humic colloids in different groundwaters is quantified by ultrafiltration as well as ultracentrifugation by the aid of radiometric concentration measurements. The speciation of dissolved Am(III) species in groundwaters is carried out by laser induced photoacoustic spectroscopy (LPAS).

Colloid Generation and the Actinide Migration in Gorleben Groundwaters

ABSTRACTThe generation and behaviour of realcolloids and pseudocolloids of the actinides, 238 pu, 241Am and 244Cm, are investigated in four different Gorleben Groundwaters. Colloids are characterized by ultrafiltration at different pore sizes from 1 nm to 450 nm and various analytical instrumentations. Behaviour of pseudocolloids has been analysed by determining their effects on the solubility and the distribution coefficient of actinides between groundwater and geomatrix. Sorption of actinide ions on groundwater-colloids (generation of pseudocolloid) are examined and the migration of actinides as pseudocolloids is discussed.