Sorption and direct speciation of neptunium(V) on aluminium oxide and montmorillonite

This study comprised batch experiments, direct speciation studies via EXAFS, and modelling with the 2SPNE SC/CE model to elucidate the mechanisms of Np(V) sorption on montmorillonite and, for reference, on γ-Al2O3. The sorption of pM 239Np(V) and µM 237Np(V) on montmorillonite (STx-1, 4 g/L) and γ-Al2O3 (0.5 g/L) was studied at room temperature in the presence and absence of ambient CO2 covering a pH-range from 2.5 (STx-1) or 5 (γ-Al2O3) to 10.5 with 0.01 or 0.1M NaClO4 as background electrolyte. The Np(V) uptake was determined by γ spectroscopy of the supernatants and calculated as percentage as well as distribution coefficient Kd. Sorption starts from pH ~6 and, under exclusion of CO2, increases continuously, while, in the presence of ambient air, it reaches a maximum at pH ~8.5 (γ-Al2O3: log Kd max ≈ 4 mL/g; STx-1: log Kd max ≈ 2.7 mL/g). Beyond that it decreases again due to the formation of queous neptunium carbonate complexes. Furthermore, neptunium sorption on montmorillonite is influenced by ionic strength at pH <6 through ion exchange processes pointing towards the formation of outer-sphere surface complexes there. Isotherms measured at the sorption maximum showed the precipitation of resumably neptunium carbonate complexes above 3∙10^-5 M under ambient air conditions. Additionally, they indicated progressive saturation of the sorption sites of γ-Al2O3. At selected pH (STx-1: 5.0, 7.0, 8.0, 8.5, 9.0, 9.5; γ-Al2O3: 8.5, 9.5) EXAFS samples were prepared as wet pastes with µM 237Np and measured at room temperature in fluorescence mode at ANKA and ESRF. Several spectra were averaged and analysed with EXAFSPAK and FEFF 8.20 employing models of NaNpO2(CO3) or soddyite, (UO2)2SiO4∙2(H2O). The shorter atomic distances of the neptunyl ion at pH 5 compared to the others hinted at the retention of the hydration shell and, thus, at outer-sphere sorption. On average the bond lengths for Np(V) sorbed on STx-1 at high pH were Oax ≈ 1.84 Å and Oeq ≈ 2.53 Å. At high pH, ternary neptunyl carbonate surface complexes could be identified for montmorillonite (C ≈ 3.00 Å), but not for γ-Al2O3, where an interaction of neptunium with the aluminium surface atoms according to the soddyite model gave better agreement with the experimental data. However, neither structure as suggested by the two models could be excluded for both systems rendering a combination most likely. Modelling of the sorption data provided further evidence for the existence of ternary neptunium carbonate surface complexes in both cases. The results of this study can aid environmental risk assessment for clay-based nuclear waste repositories by providing valuable input data for simulations of radionuclide migration from a final disposal site.

Zum Transport von partikelgebundenen Schadstoffen in der ungesättigten Zone

Bei einer Risikoabschätzung bezüglich einer Gefährdung des Schutzgutes Grundwasser müssen alle relevanten Transportpfade, auf denen Schadstoffe durch die Bodenzone bis ins Grundwasser verlagert werden, identifiziert und quantifiziert werden. Die Verlagerung von Schadstoffen gebunden an mobile Partikel im Sickerwasser wird dabei oft vernachlässigt. In dieser Arbeit wurden sowohl experimentelle Untersuchungen zum Partikeltransport in der Bodenzone als auch Szenarienmodellierungen hinsichtlich der Wechselwirkung Partikel/Schadstoff durchgeführt. Die experimentellen ungesättigten Säulenversuche wurden unter naturnahen stationären und instationären hydraulischen und hydrochemischen Bedingungen durchgeführt. Dabei wurde der Einfluss der Parameter Durchmesser Bodenmatrix, Partikelgröße, Beregnungsintensität, Oberflächenspannung und Hydrochemie auf den Transport von natürlichen und synthetischen Partikeln untersucht. Des Weiteren wurden Untersuchungen zur partikelgebundenen Verlagerung von Phenanthren durchgeführt. In einer numerischen Szenarienmodellierung mit dem Modell SMART wurde untersucht, unter welchen Randbedingungen der Transport von Partikeln gleichzeitig zu signifikanten partikelgebundenen Schadstoffkonzentrationen im Grundwasser führt. Dabei wurden die Parameter Lithologie Partikel/Boden, Hydrophobizität Schadstoff, Partikelkonzentration, Partikeldurchmesser sowie Körnung Bodenmatrix variiert. Die Ergebnisse dieser Arbeit zeigen, dass der partikelgebundene Schadstofftransportpfad in der ungesättigten Bodenzone in verschiedenen Szenarien den Anteil mobiler Schadstoffe, die mit dem Sickerwasser ins Grundwasser gelangen, signifikant erhöht. Auf Basis der experimentellen und theoretischen Untersuchungen wurde ein zweistufiges Bewertungsschema entwickelt, das bereits im Vorfeld einer Risikoabschätzung als Entscheidungshilfe hinsichtlich der Relevanz einer Mobilisierung, eines Transports und des Rückhalts von partikelgebundenen Schadstoffen in der ungesättigten Zone dient.

The release of zinc and lead from mine tailings

Mining and processing of metal ores are important causes of soil and groundwater contamination in many regions worldwide. Metal contaminations are a serious risk for the environment and human health. The assessment of metal contaminations in the soil is therefore an important task. A common approach to assess the environmental risk emanating from inorganic contaminations to soil and groundwater is the use of batch or column leaching tests. In this regard, the suitability of leaching tests is a controversial issue. In the first part of this work the applicability and comparability of common leaching tests in the scope of groundwater risk assessment of inorganic contamination is reviewed and critically discussed. Soil water sampling methods (the suction cup method and centrifugation) are addressed as an alternative to leaching tests. Reasons for limitations of the comparability of leaching test results are exposed and recommendations are given for the expedient application of leaching tests for groundwater risk assessment. Leaching tests are usually carried out in open contact with the atmosphere disregarding possible changes of redox conditions. This can affect the original metal speciation and distribution, particularly when anoxic samples are investigated. The influence of sample storage on leaching test results of sulfide bearing anoxic material from a former flotation dump is investigated in a long-term study. Since the oxidation of the sulfide-bearing samples leads to a significant overestimation of metal release, a feasible modification for the conduction of common leaching tests for anoxic material is proposed, where oxidation is prevented efficiently. A comparison of leaching test results to soil water analyzes have shown that the modified saturation soil extraction (SSE) is found to be the only of the tested leaching procedures, which can be recommended for the assessment of current soil water concentrations at anoxic sites if direct investigation of the soil water is impossible due to technical reasons. The vertical distribution and speciation of Zn and Pb in the flotation residues as well as metal concentrations in soil water and plants were investigated to evaluate the environmental risk arising from this site due to the release of metals. The variations in pH and inorganic C content show an acidification of the topsoil with pH values down to 5.5 in the soil and a soil water pH of 6 in 1 m depth. This is due to the oxidation of sulfides and depletion in carbonates. In the anoxic subsoil pH conditions are still neutral and soil water collected with suction cups is in equilibrium with carbonate minerals. Results from extended x-ray absorption fine-structure (EXAFS) spectroscopy confirm that Zn is mainly bound in sphalerite in the subsoil and weathering reactions lead to a redistribution of Zn in the topsoil. A loss of 35% Zn and S from the topsoil compared to the parent material with 10 g/kg Zn has been observed. 13% of total Zn in the topsoil can be regarded as mobile or easily mobilizable according to sequential chemical extractions (SCE). Zn concentrations of 10 mg/L were found in the soil water, where pH is acidic. Electron supply and the buffer capacity of the soil were identified as main factors controlling Zn mobility and release to the groundwater. Variable Pb concentrations up to 30 µg/L were observed in the soil water. In contrast to Zn, Pb is enriched in the mobile fraction of the oxidized topsoil by a factor of 2 compared to the subsoil with 2 g/kg Pb. 80% of the cation exchange capacity in the topsoil is occupied by Pb. Therefore, plant uptake and bioavailability are of major concern. If the site is not prevented from proceeding acidification in the future, a significant release of Zn, S, and Pb to the groundwater has to be expected. Results from this study show that the assessment of metal release especially from sulfide bearing anoxic material requires an extensive comprehension of leaching mechanisms on the one hand and on weathering processes, which influence the speciation and the mobility of metals, on the other hand. Processes, which may change redox and pH conditions in the future, have to be addressed to enable sound decisions for soil and groundwater protection and remediation.