Automated method for determining the flow of surface functionalized nanoparticles through a hydraulically fractured mineral formation using plasmonic silver nanoparticlesElectronic supplementary information (ESI) available: TEM images, UV-visible spectra, R2 fit of C and C0 curves for MSA-Ag NP and CYS-Ag NP breakthrough curves. See DOI: 10.1039/c3em00718a

Quantifying nanoparticle (NP) transport within porous geological media is imperative in the design of tracers and sensors to monitor the environmental impact of hydraulic fracturing that has seen increasing concern over recent years, in particular the potential pollution and contamination of aquifers. The surface chemistry of a NP defining many of its solubility and transport properties means that there is a wide range of functionality that it is desirable to screen for optimum transport. Most prior transport methods are limited in determining if significant adsorption occurs of a NP over a limited column distance, however, translating this to effects over large distances is difficult. Herein we report an automated method that allows for the simulation of adsorption effects of a dilute nanoparticle solution over large distances under a range of solution parameters. Using plasmonic silver NPs and UV-visible spectroscopic detection allows for low concentrations to be used while offering greater consistency in peak absorbance leading to a higher degree of data reliability and statistics. As an example, breakthrough curves were determined for mercaptosuccinic acid (MSA) and cysteamine (CYS) functionalized Ag NPs passing through Ottawa sand (typical proppant material) immobile phase (C) or bypassing the immobile phase ( C 0 ). Automation allows for multiple sequences such that the absorption plateau after each breakthrough and the rate of breakthrough can be compared for multiple runs to provide statistical analysis. The mobility of the NPs as a function of pH is readily determined. The stickiness ( α ) of the NP to the immobile phase calculated from the C / C 0 ratio shows that MSA-Ag NPs show good mobility, with a slight decrease around neutral pH, while CYS-Ag NPs shows an almost sinusoidal variation. The automated process described herein allows for rapid screening of NP functionality, as a function of immobile phase (proppant versus reservoir material), hydraulic fracturing fluid additives (guar, surfactant) and conditions (pH, temperature). Plasmonic silver nanoparticles offer a high degree of data reliability and statistics for the mobility through mineral formations.