Abteilung Wasserressourcen und Trinkwasser

The impact of phases distribution on mixing and reaction is hardly assessable experimentally. We use a multiple point statistical method, which belongs to the family of machine learning algorithms, to generate simulations of phases distributions from data out of laboratory experiments. The simulations honour the saturation of the laboratory experiments, resemble the statistical distributions of several geometric descriptors and respect the physics imposed by capillary forces. The simulated phases distributions are used to compute solute transport. The breakthrough curves reveal that different phases distributions lead to broad ranges of early arrival times and long-term tailings as saturation decreases. For a given saturation, a similar long-term scaling of mixing area, interface length, and corresponding reactivity is observed regardless of phases distribution. However, phases distribution has a clear impact on the final values (before breakthrough) of area of mixing, interface length and mass of reaction product.

The photolytic chlorination of n-alkanes in presence of sulfuryl chloride (SO₂Cl₂) was explored to produce new standard materials. Five mixtures of chlorinated tetradecanes were synthesized with chlorination degrees (m_Cl,EA) varying from 43.7% to 59.4% (m/m) based on elemental analysis. Chlorine-enhanced negative chemical ionization mass spectrometry (CE–NCI–MS) forcing the formation of chloride-adduct ions [M+Cl]^- was applied to characterize these materials which all contained tetra-to deca-chlorinated paraffins. Deconvolution of respective mass spectra revealed the presence of chlorinated olefins (COs). CO levels were highest in materials, which were exposed longest. All synthesized materials also contained two classes of polar impurities, tentatively assigned as sulfite- and sulfate-diesters with molecular formulas of C₁₄H_28-xO₃SCl_x (x = 1-4) and C₁₄H_28-xO₄SCl_x (x = 3–6), respectively. MS data were in accordance with the proposed structures but further work is needed to deduce their constitutions. These compounds are thermolabile and were not detected with GC-MS methods. We could remove these sulfur-containing impurities from the CPs with normal-phase liquid chromatography. In conclusion, single-chain CP materials were synthesized via chlorination of n-alkanes with sulfuryl chloride, but these materials contained reactive side products which should be removed to gain non-reactive and stable CP materials suitable as standards and for fate and toxicity studies.

We investigate the impact of pore-scale heterogeneity on reactive mixing using experimental data from inert fluid-fluid displacement in a quasi 2-D porous medium. We interpret the invading and defending fluids as the conservative components A + C and B + C of the instantaneous irreversible bimolecular chemical reaction A + B → C and determine the reaction product C . We find strong growth of the reaction rate at short and intermediate times due to deformation of the mixing interface and heterogeneity-induced increase of the mixing area. This behavior is captured by a dispersive lamella approach that quantifies the mixing dynamics at the interface in terms of temporally evolving effective dispersion coefficients. The latter capture the dominant controls on the evolution of the mixing interface, namely, advective heterogeneity and transverse mixing. Reactive transport formulations based on constant hydrodynamic dispersion coefficients are not able to describe the observed behavior due to the lack of complete mixing on the support scale, which is required for these approaches to hold. These results shed some new light on the origins of heterogeneity-induced mixing and reaction dynamics in porous media and their systematic upscaling.