Improved Methodology for the Extraction of Nanoparticles and Colloids from Agricultural Soils: Ultrasound-Assisted, Continuous-Flow Extraction and Characterization by Single Particle Inductively Coupled Plasma Mass Spectrometry

In soils, it is key to not simply determine the behavior of the major elements but also understand the fate of trace and ultra-trace elements that can often have disproportionate effects on these complex systems. Soils, including agricultural soils, constitute a reservoir of nanoparticles and natural colloids of multiple origins. Nonetheless, only limited information is available on the concentrations and fate of nanoparticles in soils, due largely to the difficulty of distinguishing anthropogenically generated particles from the complex soil matrices in which they are found. Bulk measurements are often unable to quantify the key contributions of trace pollutants (i.e., needle in a haystack); however, single particle techniques have recently become available for studying complex agricultural systems, including soils. For example, the characterization of engineered nanoparticles or incidentally generated particulate pollutants within a natural soil or sediment is now possible using techniques such as single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). Nonetheless, in order to exploit the single particle techniques, it is first necessary to representatively sample the soils. The approach presented here has been designed to help better understand the impact of incidental and engineered nanoparticles on agricultural soils. In this study, we examine two approaches for extracting colloidal particles (CP) from soils in order to facilitate their characterization by single particle inductively coupled plasma mass spectrometry using a sector field- (SP-ICP-SF-MS) and time-of-flight- (SP-ICP-ToF-MS) based instruments. A novel sampling methodology consisting of an ultrasound-assisted continuous-flow extraction (USCFE) was developed and compared to a commonly used batch extraction procedure. Metal containing colloidal particles (M–CP) were quantified and characterized following their extraction in ultrapure water and tetrasodium pyrophosphate (TSPP). At least five successive extraction cycles of 18 h each were required to optimally extract Si–CP (ca. 6 × 1015 kg−1) using the batch extraction approach, whereas similarly high numbers of CP could be extracted by USCFE in about 3 h. The combined use of continuous flow, ultrasound and TSPP improved the sampling of colloidal particles and nanoparticles from an agricultural soil. Due to its higher sensitivity, SP-ICP-SF-MS was used to measure the smallest detectable M–CP in the soil extracts. SP-ICP-ToF-MS was used to determine the multi-elemental composition of the extracted colloidal particles.