Silver nanoparticles (AgNPs) are highly produced in developed countries for a variety of products. Consequently, AgNPs end up being introduced in aquatic systems all over the world, and usually deposited in riverine sediments, from where they can be taken up by aquatic organisms and transferred along the food chain. The analysis of AgNPs in natural samples is not an easy task, because of their low presence and complicated reactions, which can change their speciation. The objective of this work is to help in this challenge, developing a method applicable to analyse sediment samples from any place around the world where AgNPs are suspected to be present. Firstly, four methods for the synthesis of AgNPs were investigated by Ultraviolet-visible (UV-VIS) spectroscopy and particle size analysis. The methods differed in the reducing agent used and in the concentration of the stabilising agent applied. The method including NaBH4 and SDS (sodium dodecyl sulphate) resulted to be more adequate as the Surface Plasmon Resonance (SPR) band position and width indicated. This conclusion was corroborated considering the hydrodynamic diameters and polydispersity indices of the synthesised AgNPs. The Z-average hydrodynamic diameter and the UV-VIS spectrum of AgNPs synthesised using this method indicated that the AgNPs remained kinetically stable for at least 10 days. Finally, ten potential extraction solutions were investigated, in terms of maximal extraction efficiency, but minimal effects on AgNP dissolution and aggregation. The candidate solutions ranged from deionized water and salts to strong acids and bases. The intensity of the SPR band concluded that using NaOH media the synthesised AgNPs was kinetically stable. Moreover, TEM (Transmission Electron Microscopy) images showed that the AgNPs in NaOH retained their shape and size after 10 days. Therefore, NaOH media turned out to be the best potential extractant for the analysis of sediment samples.