Karsten Heim

Extracellular Polymeric Substances Govern the Surface Charge of Biogenic Elemental Selenium Nanoparticles

The origin of the organic layer covering colloidal biogenic elemental selenium nanoparticles (BioSeNPs) is not known, particularly in the case when they are synthesized by complex microbial communities. This study investigated the presence of extracellular polymeric substances (EPS) on BioSeNPs. The role of EPS in capping the extracellularly available BioSeNPs was also examined. Fourier transform infrared (FT-IR) spectroscopy and colorimetric measurements confirmed the presence of functional groups characteristic of proteins and carbohydrates on the BioSeNPs, suggesting the presence of EPS. Chemical synthesis of elemental selenium nanoparticles in the presence of EPS, extracted from selenite fed anaerobic granular sludge, yielded stable colloidal spherical selenium nanoparticles. Furthermore, extracted EPS, BioSeNPs, and chemically synthesized EPS-capped selenium nanoparticles had similar surface properties, as shown by ζ-potential versus pH profiles and isoelectric point measurements. This study shows that the EPS of anaerobic granular sludge form the organic layer present on the BioSeNPs synthesized by these granules. The EPS also govern the surface charge of these BioSeNPs, thereby contributing to their colloidal properties, hence affecting their fate in the environment and the efficiency of bioremediation technologies.

The complexation of uranium(VI) and atmospherically derived CO2 at the ferrihydrite-water interface probed by time-resolved vibrational spectroscopy.

The sorption reactions of uranium(VI) at the ferrihydrite(Fh)-water interface were investigated in the absence and presence of atmospherically derived CO(2) by time-resolved in situ vibrational spectroscopy. The spectra clearly show that a single uranyl surface species, most probably a mononuclear bidentate surface complex, is formed irrespective of the presence of atmospherically derived CO(2). The character of the carbonate surface species correlates with the presence of the actinyl ions and changes from a monodentate to a bidentate binding upon sorption of U(VI). From the in situ sorption experiments under mildly acid conditions, the formation of a ternary surface complex is derived where the carbonate ligands coordinate bidentately to the uranyl moiety (≡UO(2)(O(2)CO)(x)). Furthermore, the release reaction of the carbonate ligands from the ternary surface complex is found to be considerably retarded compared to those from the pristine surface suggesting a tighter bonding of the carbonate ions in the ternary complex. Simultaneous sorption of U(VI) and atmospherically derived carbonate onto pristine Fh shows formation of binary monodentate carbonate surface complexes prior to the formation of the ternary complexes.

Probing the surface speciation of uranium (VI) on iron (hydr)oxides by in situ ATR FT-IR spectroscopy.

The surface speciation of uranium(VI) on maghemite (γ-Fe2O3) was elucidated at the spectroscopic level for the first time. By means of in situ ATR FT-IR measurements, the formation of uranium(VI) outer-sphere complexes was revealed under anoxic conditions and in ambient atmosphere at mildly acid conditions. This type of complexation was verified by the frequency of the ν3(UO2) mode observed for the surface species, the impact of the ionic strength of the background electrolyte on U(VI) sorption and by the high reversibility of the sorption process monitored by on line spectroscopy. The impact of carbonate ions from atmospherically derived CO2 on U(VI) sorption on maghemite was investigated. Although the surface speciation of the carbonate ions presumably change from a monodentate coordination on maghemite to a bidentate coordination in the ternary sorption system, the U(VI) speciation is not changed. A contrasting juxtaposition of comparable results obtained from maghemite and ferrihydrite reveals a basically different type of U(VI) complexation, namely outer and inner spheric coordination.

Complex Formation of Uranium(VI) with L-Phenylalanine and 3-Phenylpropionic Acid Studied by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy

Uranyl complexes with phenylalanine and the analogous ligand phenylpropionate were investigated in aqueous solution by attenuated total reflection (ATR) Fourier transform infrared (FT-IR) spectroscopy. The assignment of the observed bands to vibrational modes was accomplished using spectra of the pure ligands recorded at different pH values and spectra of the 15N labeled analogous compounds of the amino acid. The results presented in this work provide a detailed description of the binding states of the uranyl complexes in solution. A bidentate binding of the carboxylate group to the actinide ion was observed by the characteristic shifts of the carboxylate modes. From the spectra the presence of the protonated amino group in the actinide complex can be derived. Due to these findings, contributions of the amino group to the binding to the uranyl ion in the amino acid complex can be ruled out.

Selenium(IV) Sorption Onto γ-Al2O3: A Consistent Description of the Surface Speciation by Spectroscopy and Thermodynamic Modeling

The sorption processes of Se(IV) onto γ-Al2O3 were studied by in situ Infrared spectroscopy, batch sorption studies, zeta potential measurements and surface complexation modeling (SCM) in the pH range from 5 to 10. In situ attenuated total reflection fourier-transform infrared (ATR FT-IR) spectroscopy revealed the predominant formation of a single inner-sphere surface species at the alumina surface, supporting previously reported EXAFS results, irrespective of the presence or absence of atmospherically derived carbonate. The adsorption of Se(IV) decreased with increasing pH, and no impact of the ionic strength was observed in the range from 0.01 to 0.1 mol L-1 NaCl. Inner-sphere surface complexation was also suggested from the shift of the isoelectric point of γ-Al2O3 observed during zeta potential measurements when Se(IV) concentration was 10-4 mol L-1. Based on these qualitative findings, the acid-base surface properties of γ-Al2O3 and the Se(IV) adsorption edges were successfully described using a 1-pK CD-MUSIC model, considering one bidentate surface complex based on previous EXAFS results. The results of competitive sorption experiments suggested that the surface affinity of Se(IV) toward γ-Al2O3 is higher than that of dissolved inorganic carbon (DIC). Nevertheless, from the in situ experiments, we suggest that the presence of DIC might transiently impact the migration of Se(IV) by reducing the number of available sorption sites on mineral surfaces. Consequently, this should be taken into account in predicting the environmental fate of Se(IV).

Adsorption of selenium(VI) onto nano transition alumina

The adsorption of selenium(VI) onto nano transition alumina (γ/δ-Al2O3) was investigated at both macroscopic and molecular levels. The uptake of selenium(VI) was found to decrease upon increasing pH (5–10) and ionic strength (0.01–0.1 mol L−1 NaCl). At the molecular level, in situ attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy established the predominant formation of a bidentate outer-sphere surface complex throughout the investigated pH range. The acid–base surface properties of transition alumina (surface charge) together with the Se(VI) adsorption edges were successfully described using a 1-pK charge distribution surface complexation model involving one outer-sphere selenium(VI) surface species, namely {(AlOH20.5+)2SeO42−} as suggested by the IR studies. Blind predictions of literature data yielded good agreement in particular in NaCl systems. These new spectroscopy based results can be implemented in reactive transport models to enable more consistent and trustworthy prognostic modeling of the environmental fate of selenium(VI).