Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca. The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled.

The transport and retention behavior of polymer-(PVP-AgNP) and surfactant-stabilized (AgPURE) silver nanoparticles in carbonate-dominated saturated and unconsolidated porous media was studied at the laboratory scale. Initial column experiments were conducted to investigate the influence of chemical heterogeneity (CH) and nano-scale surface roughness (NR) arising from mixtures of clean, positively charged calcium carbonate sand (CCS), and negatively charged quartz sands. Additional column experiments were performed to elucidate the impact of CH and NR arising from the presence and absence of soil organic matter (SOM) on a natural carbonate-dominated aquifer material. The role of the nanoparticle capping agent was examined under all conditions tested in the column experiments. Nanoparticle transport was well described using a numerical model that facilitated blocking on one or two retention sites. Results demonstrate that an increase in CCS content in the artificially mixed porous medium leads to delayed breakthrough of the AgNPs, although AgPURE was much less affected by the CCS content than PVP-AgNPs. Interestingly, only a small portion of the solid surface area contributed to AgNP retention, even on positively charged CCS, due to the presence of NR which weakened the adhesive interaction. The presence of SOM enhanced the retention of AgPURE on the natural carbonate-dominated aquifer material, which can be a result of hydrophobic or hydrophilic interactions or due to cation bridging. Surprisingly, SOM had no significant impact on PVP-AgNP retention, which suggests that a reduction in electrostatic repulsion due to the presence of SOM outweighs the relative importance of other binding mechanisms. Our findings are important for future studies related to AgNP transport in shallow unconsolidated calcareous and siliceous sands.

&lt;p&gt;Nowadays engineered silver nanoparticles (AgNP) are being widely used for a multitude of purposes. At certain times during their life-cycle they might enter soils and freshwater resources and thus recent research has focused on their transport and fate in soils and the vadose zone as well as the saturated zone. AgNP retention in the subsurface depends on a multitude of parameters including the type and shape of the sediments through the nanoparticles are exposed to, the chemical composition of pore and groundwater acting as background solution or the type and quantity of soil organic matter present. One aspect that has received little attention so far is their transport behaviour in the presence of nutrients.&lt;/p&gt;&lt;p&gt;Here we study PVP-AgNP transport and retention in saturated columns containing silicate-dominated aquifer material that is also exposed to orthophosphate (NaH&lt;sub&gt;2&lt;/sub&gt;PO&lt;sub&gt;4&lt;/sub&gt;) or &lt;em&gt;myo&lt;/em&gt;-inositol hexakisphosphate (IP6) via the background solution. In particular, we compare PVP-AgNP transport behaviour for different pH (6 and 4.5) in the background solution, for different mass concentrations of sediments &lt;63 &amp;#181;m in the columns (0 and 2%) and in the presence/absence of soil organic matter (SOM). Experimental data were modelled using HYDRUS 1D.&lt;/p&gt;&lt;p&gt;Results of our experiments show that PVP-AgNP exhibit a higher mobility through the columns in the presence of phosphate as the latter can block attachment sites otherwise available to the nanoparticles. In the presence of SOM this mobility is even higher than in the absence of SOM as SOM and phosphate anions are both negatively charged and potentially bound to the same attachment sites. PVP-AgNP mobility also increased for both P-species when an increase in pH occurred but this increase was more pronounced in columns with orthophosphate. Results further show that PVP-AgNP are more mobile in columns with IP6 than orthophosphate in the absence of sediments &lt;63 &amp;#181;m at pH 4.5. However, while for columns with material &lt; 63 &amp;#181;m the overall AgNP mobility is decreased due to an overall increase in sediment surface area, AgNP are more mobile in the presence of orthophosphate as IP6 is more strongly bound to iron and aluminium oxides found in higher abundance in the fine sediments. &amp;#160;&amp;#160;&lt;/p&gt;