No abstract

No abstract

Summary The mobility of goethite (OMCG) colloids coated with organic matter was studied in goethite‐coated quartz sand and in undisturbed subsoil rich in natural coatings of iron oxide. Classic Derjaguin–Landau–Verwey–Overbeek (DLVO) interactions and DLVO extended by Lewis acid–base parameters (XDLVO) were estimated between colloids and goethite‐coated sand from zeta potentials and sessile drop contact angles. The OMCG colloids were retained completely in goethite‐coated sand, whereas preconditioning of the solid matrix with dissolved organic matter (DOM) enabled subsequent colloid transport. Zeta potential values showed that goethite‐coated sand was modified strongly by DOM preconditioning. The DLVO and XDLVO interactions were estimated for the pairs of OMCG colloids and for (i) quartz, (ii) goethite and (iii) organic matter‐coated goethite. Both DLVO approaches were able to predict general trends of colloid breakthrough. An exception was the XDLVO interaction for combination (iii), which showed short‐distance (<1.3 nm) repulsive interactions that were inconsistent with breakthrough behaviour. Analogous to OMCG colloid transport in the sand, DOM preconditioning was also the prerequisite for OMCG colloid transport in undisturbed subsoil. Total colloid breakthrough in the soil was less than in the sand, probably because of straining in pore throats and retention at air–water interfaces. We concluded that the DLVO and XDLVO approaches were in general capable of predicting trends of OMCG colloid mobility in goethite‐coated sand. We concluded further that the basic principles of OMCG colloid transport were transferrable from the simplified model system to the more complex natural system despite considerable differences in surface properties, pore structure and water content. Highlights How will organic matter (OM) coatings on the solid matrix affect mobility of iron oxide colloids? Effect of OM on mobility was assessed in simple model soil systems and in undisturbed soil. OM coatings modify properties of the solid matrix surface and are a prerequisite for colloid transport. Balances between OM transport, coating formation and decomposition control colloid mobility.

The influence of porous media wettability on the mobility of colloids is mostly unknown. In the present work, organic-matter-coated goethite (OMCG) colloids were percolated through three saturated soil materials differing in wettability: untreated quartz sand and two variants of hydrophobized sand. For each type of sand, three ionic strength levels were applied. Derjaguin-Landau-Verwey-Overbeek (DLVO) and Lewis acid-base extended DLVO (XDLVO) interaction energy profiles were calculated according to contact angles and zeta potentials. Flow column results elucidated that decreasing sand wettability had no relevant effect on OMCG colloid mobility. In contrast, colloid retention increased with ionic strength in each type of sand packing. Classic DLVO interactions could predict trends in colloid retention by the respective characteristics of energy barriers and secondary minima. The extension with Lewis acid-base interactions in the XDLVO approach led to the prediction of significant short-range (?2 nm) attractive interaction energies between colloids and hydrophobized sand, which were not reflected by colloid breakthrough behavior. This was probably due to substantial energy barriers calculated for larger distances (?27 to ?75 nm, depending on ionic strength) between the solid matrix and colloids. It is concluded that the distinct surface roughness of sand grains and colloids probably weakened the strength of the short-range attractive interactions, because larger amounts of surface area were still outside the effective distance for the short-range interactions predicted by XDLVO. Regarding colloidal mobility, we concluded for our saturated porous systems that near-surface attractive XDLVO interaction energies between OMCG colloids and hyrophobized sand did not significantly affect colloid mobility.

&lt;p&gt;Dissolved organic matter (DOM) is one of the most mobile components of the global carbon cycle. Corresponding transport processes in the environment have received plenty of attention in the context of carbon sequestration as well as the mobility of DOM-associated contaminants.&lt;/p&gt;&lt;p&gt;However, most previous transport studies have been conducted exclusively under continuous flow conditions, which are not comparable to real water flow characteristics in soil. The present study aims to address that gap in knowledge by systematically assessing the effect of defined flow interruption phases on the retention of DOM.&lt;/p&gt;&lt;p&gt;For that, the breakthrough behavior of DOM as affected by phases of flow interruption was investigated in an increasingly complex system of solid matrices rich in oxide mineral coatings: goethite coated quartz sand, disturbed Cambisol subsoil, and undisturbed Cambisol subsoil. The classic DLVO and extended DLVO (XDLVO) models including Lewis acid&amp;#8212;base parameters were applied based on measurements of sessile drop contact angles and zeta potentials. &amp;#160;&lt;/p&gt;&lt;p&gt;DOM retention was increasing with the duration of flow interruption, and retention was considerably higher in the soils than in goethite coated sand. After 112 hours of flow stagnation, DOM release from the soils was reduced to 16 to 22 % as compared to continuous flow conditions. The retention in the different solid matrix materials was well correlated with the respective amounts of oxalate and dithionite extractable oxide mineral phases. The DLVO model was capable of correctly predicting the mobility of DOM in goethite coated sand, but not in the soils, due to the fact that soil surface charge heterogeneities could not be measured. The XDVLO model predicted short-range hydrophilic repulsive interactions that may have contributed to the distinct tailing of the DOM breakthrough curves.&lt;/p&gt;&lt;p&gt;We conclude that the significant DOM retention during phases of flow stagnation phases shows that more complex flow regimes need to be considered in order to assess the mobility of DOM in soils. In fact, many previous studies excluding phases of flow stagnation likely overestimated the mobility of DOM in the environment.&lt;/p&gt;