Publikationen

doi.org/10.1038/s40494-026-02358-1

Abstract
Petroglyphs on Murujuga in northwest Western Australia depict 50,000+ years of the culture and spiritual beliefs of humankind. They are sacred for the indigenous people. These priceless and irreplaceable petroglyphs are threatened by acidic gas and nitrogenous pollutants from natural gas and chemical facilities. Preservation of the rock surface ferromanganese layer is crucial for survival of the petroglyphs. Rock surface pH has fallen from neutral pre-industrialisation to 4.4–5.2 adjacent to industry. We separated surface material from Murujuga rocks, ground it finely, and subjected the powders to increasing concentrations of inorganic compounds emitted by industry and to organic acids from organisms stimulated by pollutants. Statistical analyses revealed the release of elements crucial for maintaining the integrity of the ferromanganese layer commenced at pH values well above rock surface measurements. Preservation of the globally unique petroglyphs on Murujuga requires urgent introduction of available technologies to reduce industrial emissions to zero.

doi.org/10.3791/67763

Abstract
Fluid-cell Raman Spectroscopy (FCRS) enables the real-time and space-resolved (operando) study of reaction mechanisms, kinetics, and their mutual interactions with transport processes during silicate glass corrosion at the micrometer scale and at elevated temperatures. This manuscript provides a detailed protocol for setting up an FCRS experiment, exemplified by a corrosion experiment with a ternary Na borosilicate glass and a 0.5 M NaHCO3 solution at a temperature of 86 ± 1 °C. The protocol involves (i) sample preparation, (ii) assembly of the fluid cell, and (iii) setting of Raman measurement parameters for collecting Raman spectra across the sample/solution interface in regular time intervals. The results from the experiment show the formation of a water-rich zone between a silica-based surface alteration layer (SAL) and the pristine glass, which is an intrinsic feature of an interface-coupled dissolution-precipitation model for the formation of a SAL during silicate glass corrosion. The ability to track the reaction and transport processes during the corrosion of silicate glasses and potentially of other transparent materials, spatially resolved and in real-time, represents a unique strength of this technique, overcoming the disadvantages of conventional analysis of multi-step quenching experiments. The corrosion of the top side of the glass sample represents a current issue, reducing spatial resolution at depth due to precipitation within the laser pathway. This is caused by a solution-filled gap between the sapphire window of the fluid cell lid and the top side of the monolith, which is difficult to avoid during the experimental setup. This must be taken into account when choosing the depth at which the measurement should be made. In a few cases, the formation of air bubbles was observed, which disrupted or even led to the termination of the experiment. However, this can be avoided by carefully setting up the experiment, which requires little practice.

doi.org/10.1016/j.pnucene.2023.104796

Abstract
Detailed understanding about the chemical and physical properties of the Chernobyl “lava” and other radioactive meltdown products is of paramount importance for the support of decommissioning operations and nuclear accident modelling. In this study, we provide new results about the chemical composition and structural properties of the Chernobyl “lava” matrix obtained by electron microprobe analysis and confocal Raman spectroscopy. Based on the compositional data, a principal component analysis (PCA) was conducted to visualize compositional features of the black and brown “lava”, considering data from previous studies. In addition, an inverse modelling approach was performed to assess fractional contributions of construction materials that potentially contributed to the “lava” formation process. The results of the PCA show three varieties of “lava”. Different fractional contributions of UO2-fuel and Zr-cladding indicate the formation of at least two distinct sources of coium melt, respectively, for the black and brown “lava”. For the brown “lava”, the high concentration of Mg is explained by the melting and assimilation of 23% serpentine stemming from the lower reactor shield. The black “lava” shows a high contribution of concrete (43%). Significant differences in the Fe concentration of the black “lava”, as well as macroscopic flow patterns are indicative for a progressive melt formation. However, the cooling of the “lava” occurred relatively fast, forming a metaluminous glass with local variations in the degree of polymerization. Sub-microscopic inclusions of (U1-xZrx)O2 and (Zr1-xUx)O2 solid solutions point to a fractionation of U from an highly oversaturated melt. Based on the new results, the current hypothesis about the “lava” formation process is discussed and reviewed, questioning the existence of one homogenous source of melt and its stratification into layers of black and brown “lava”, before spreading and solidification of the melt.

doi.org/10.1016/j.gca.2022.05.013

Abstract
Mechanisms, feedbacks and resulting non-linearity during silicate glass alteration in a hyperalkaline carbonate solution were studied through hyperspectral Raman imaging of heated fluid-cells. Our experimental setup enabled in operando visualization and rate measurements of glass dissolution and secondary phase precipitation, complemented by spectral characterization of the phases involved and semi-quantitative monitoring of the ionic strength of the solution close to the glass interface. After initial congruent dissolution of the Ba-bearing soda-lime boroaluminosilicate glass, the formation of a crystalline, saponite-based surface alteration layer (SAL), as well as subsequent zeolite precipitation, witherite coating, and carbonate precipitation within pore spaces of the saponite layer were observed. Two in operando experiments were conducted at ∼ 90 °C for 180 and 260 h that otherwise solely differed in the solution volume (SV) while keeping the surface area constant. The high SV experiment exhibited a transient upward excursion of initial dissolution rates, followed by continuously rapid glass dissolution along with slow SAL growth and sustained oscillations in ionic strength. Contrastingly, in the low SV experiment, glass dissolution monotonically decreased after the onset of rapid SAL growth and no sustained oscillations were observed. We find that growth conditions and resulting properties of the SAL exert dominant, non-linear effects on the evolution of glass dissolution rates. In turn, SAL formation depends on nucleation/growth kinetics and the accumulation of glass-derived solutes at the reaction front. Both, dissolution and precipitation, feedback with solution chemistry and transport processes, together controlling the evolution of the corrosion process. Additionally, fracturing, delamination, and the evolution of surface morphology may affect glass dissolution rates and transport pathways. Such interpretations of decelerating reaction rates in response to the growth of a protective layer are consistent in micro-scale experiments and in outcrop- to global-scale observations, as is the accelerating effect of surface area creation by physical disruption and morphology. Thus, these µm-scale mechanistic insights could help elucidating local to global environmental feedbacks (e.g., erosion or weathering patterns) as well as process dynamics in engineered environments (e.g., nuclear waste disposal) and may assist the improvement predictive models.

doi.org/10.1007/s10853-022-07570-5

Abstract
Silica-/calcium phosphate ceramics are of high interest in various aspects. On the one hand, they play an important role in medical applications due to their excellent biocompatibility. Therefore, detailed knowledge of the formation and stability properties of the high-temperature products ensures production under controlled conditions. On the other hand, they were identified as sinter deposits in industrial kilns, where it can indicate problems caused by too high combustion temperatures during the thermal combustion processes. Here, we report the results of two Raman heating studies to ~ 1300 °C in 10 °C-steps with nano-crystalline hydroxylapatite (HAp) and tricalcium phosphate (TCP), and a Raman heating study of natural silicocarnotite (to ~ 1200 °C, 50 °C-steps). The Raman experiments were complemented with thermal analyses. The Raman spectra of nano-crystalline HAp recorded at high temperatures revealed the stepwise loss of adsorbed water and surface-bound OH groups until ~ 570 °C. Significant loss of structural OH started at ~ 770 °C and was completed at ~ 850 °C, when HAp transformed to β-TCP. Between ~ 1220 and ~ 1270 °C, β-TCP was found to transform to α-TCP. The room temperature Raman spectrum of silicocarnotite is characterized by an intense v1(PO4) band at 951 ± 1 cm−1 that shifts to ~ 930 cm−1 at ~ 1200 °C. Using hyperspectral Raman imaging with a micrometer-scale spatial resolution, we were able to monitor in operando and in situ the solid-state reactions in the model system Ca10(PO4)6(OH)2-SiO2-CaO, in particular, the formation of silicocarnotite. In these multi-phase experiments, silicocarnotite was identified at ~ 1150 °C. The results demonstrate that silicocarnotite can form by a reaction between β-TCP and α′L-Ca2SiO4, but also between β-TCP and CaSiO3 with additional formation of quartz.

doi.org/10.1186/s40494-022-00706-5

Abstract
Murujuga in Western Australia has the largest concentration of ancient rock engravings (petroglyphs) in the world. However, the Murujuga rock art is potentially threatened by local industrial air pollution, in particular by acid rain, but unambiguous scientific evidence is still missing. Here, we report on results of an accelerated weathering experiment, simulating Murujuga weather and climate conditions that was designed and performed to test whether the expected small changes in chemical, mineralogical, and physical characteristics of the rock surface can be detected and reliably quantified by various analytical means. Locally acquired Murujuga granophyre and gabbro samples with natural varnish were artificially weathered for up to four months in a climate chamber under conditions that simulated 2 years of natural weathering. Mineralogical, chemical, and physical changes were qualitatively monitored by X-ray diffraction and confocal Raman spectroscopy, and quantified by colorimetry, portable X-ray fluorescence spectrometry, and micro-computed tomography. In addition, artificial rainwater that was sprinkled over the rock samples was collected and analysed by inductively-coupled plasma mass spectrometry. The results show significant chemical and physical changes of the surfaces of the rock varnish after 1 month of artificial weathering. The analytical results demonstrate that it is possible to quantitatively monitor small changes caused by the weathering of gabbro and granophyre. Therefore, such a semi-actualistic experimental approach, when carefully designed, potentially allows testing the hypothesis that the weathering rate of the Murujuga petroglyphs is increased by local industrial air pollution. Further experimental work is currently under way.

doi.org/10.1038/s41563-019-0293-8

Abstract
Borosilicate glass is an important material used in various industries due to its chemical durability, such as for the immobilization of high-level nuclear waste. However, it is susceptible to aqueous corrosion, recognizable by the formation of surface alteration layers (SALs). Here, we report in situ fluid-cell Raman spectroscopic experiments providing real-time insights into reaction and transport processes during the aqueous corrosion of a borosilicate glass. The formation of a several-micrometre-thick water-rich zone between the SAL and the glass, interpreted as an interface solution, is detected, as well as pH gradients at the glass surface and within the SAL. By replacing the solution with a deuterated solution, it is observed that water transport through the SAL is not rate-limiting. The data support an interface-coupled dissolution–reprecipitation process for SAL formation. Fluid-cell Raman spectroscopic experiments open up new avenues for studying solid–water reactions, with the ability to in situ trace specific sub-processes in real time by using stable isotopes.

doi.org/10.3390/app9071310

Abstract
In the last decades, Raman spectroscopy has become an important tool to identify and investigate minerals, gases, glasses, and organic material at room temperature. In combination with high-temperature and high-pressure devices, however, the in situ investigation of mineral transformation reactions and their kinetics is nowadays also possible. Here, we present a novel approach to in situ studies for the sintering process of silicate ceramics by hyperspectral Raman imaging. This imaging technique allows studying high-temperature solid-solid and/or solid-melt reactions spatially and temporally resolved, and opens up new avenues to study and visualize high-temperature sintering processes in multi-component systems. After describing in detail the methodology, the results of three application examples are presented and discussed. These experiments demonstrate the power of hyperspectral Raman imaging for in situ studies of the mechanism(s) of solid-solid or solid-melt reactions at high-temperature with a micrometer-scale resolution as well as to gain kinetic information from the temperature- and time-dependent growth and breakdown of minerals during isothermal or isochronal sintering.

doi.org/10.3390/ma12091480

Abstract
Borosilicate glasses are the favored material for immobilization of high-level nuclear waste (HLW) from the reprocessing of spent fuel used in nuclear power plants. To assess the long-term stability of nuclear waste glasses, it is crucial to understand how self-irradiation affects the structural state of the glass and influences its dissolution behavior. In this study, we focus on the effect of heavy ion irradiation on the forward dissolution rate of a non-radioactive ternary borosilicate glass. To create extended radiation defects, the glass was subjected to heavy ion irradiation using 197Au ions that penetrated ~50 µm deep into the glass. The structural damage was characterized by Raman spectroscopy, revealing a significant depolymerization of the silicate and borate network in the irradiated glass and a reduction of the average boron coordination number. Real time, in situ fluid-cell Raman spectroscopic corrosion experiments were performed with the irradiated glass in a silica-undersaturated, 0.5 M NaHCO3 solution at temperatures between 80 and 85 °C (initial pH = 7.1). The time- and space-resolved in situ Raman data revealed a 3.7 ± 0.5 times increased forward dissolution rate for the irradiated glass compared to the non-irradiated glass, demonstrating a significant impact of irradiation-induced structural damage on the dissolution kinetics.

doi.org/10.3389/feart.2016.00064

Abstract
The monazite-type solid solution of LaPO4 and EuPO4 has been studied by X-ray diffraction, infrared (IR) and Raman spectroscopic techniques. A substantial excess molar volume has been derived from the X-ray data, and the Raman and IR spectra show band broadening typical for mixing of cations of different size on the cation sublattice. The IR spectra were interpreted by the autocorrelation method and the excess autocorrelation parameter Δcorrex shows clear deviation from ideal solution behavior, similar to the observed broadening of the Raman bands. The results can be interpreted in terms of local lattice strains resulting from the ion size effects of substitution of La3+ by Eu3+, and correlate very well with calorimetric measurements of the excess enthalpy that was previously measured.

doi.org/10.1016/j.jnucmat.2010.12.218

Abstract
A comprehensive study on the aqueous stability of Ce- and Pu-doped zirconolite has been performed. Four series of hydrothermal experiments were carried out with Ce-doped zirconolite powders: (1) a solution series (1 M HCl, 2 M NaCl, 1 M NaOH, 1 M NH3, pure H2O), (2) a temperature series (T = 100–300 °C), (3) a surface area-to-fluid volume ratio series, and (4) a series using different reactor materials (Teflon©, Ni, and Ag). In addition, experiments on 238Pu- and 239Pu-doped zirconolite ceramics in a 1 M HCl solution have been performed. The 238Pu-doped zirconolite had already accumulated significant radiation damage and was X-ray amorphous, while the 239Pu-doped zirconolite was still well-crystalline. The results of the different experimental series can be summarized as follows: (1) After 14 days the degree of alteration is insignificant for all solutions other than 1 M HCl, which was therefore used for all other experimental series; (2) TiO2 and m-ZrO2 replaced the zirconolite grains to varying degrees in the 1 M HCl solution, i.e., zirconolite dissolution is incongruent; (3) the degree of alteration increases only slightly with increasing temperature; (4) the alteration rate is independent on the surface to volume ratio; (5) Ag dissolved from the silver reactors dramatically increases the reaction rate, while Ni from the Ni reactors reduces the solubility of Ti and Zr in the HCl solution, indicating that background electrolytes have a strong effect on the alteration rate. From the experiment with the Pu-doped samples at 200 °C in a 1 M HCl solution it was found that the amorphous 238Pu-doped zirconolite was altered to a significantly greater extent than the crystalline counterparts. The results suggest a coupled dissolution-reprecipitation mechanism, which is discussed in detail.

doi.org/10.2113/gselements.3.1.43

Abstract
Natural zircon crystals often show complex secondary textures that cut across primary growth zones. In zircon showing structural damage caused by self-irradiation, such textures are the result of a diffusion-reaction process in which a hydrous species diffuses inwards and “catalyzes” structural recovery. Nanoscale pores develop, solvent elements such as Ca, Al and Fe are gained, and radiogenic Pb is lost. In both aqueous fluids and melts, replacement of zircon with undamaged structure by a coupled dissolution-reprecipitation process can produce similar textures. The reacted domains usually have lower trace element contents and may contain micrometer-sized pores and inclusions of uranium, thorium and/or yttrium phases, originally in solid solution. Both processes have considerable implications for zircon geochronology.