Detection of microplastics in environmental samples requires fast, sensitive and selective analytical techniques, both in terms of the size of the microparticles and their concentration. Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) allows the detection of plastic particles down to ca. 1 µm and down to concentrations of 100 particles per mL. In SP-ICP-MS, detection of carbon-containing particles is hampered by the presence of other forms of carbon (carbonates, organic matter, microorganisms…). An acidic pre-treatment of river water samples with 10% (v/v) nitric acid for 24 h allowed the reduction of the presence of dissolved carbon to ultrapure water levels and the digestion of potential microorganisms in the samples, recovering polystyrene microparticles up to 80%. Carbon-containing particles were detected in most of the samples analysed from Spanish and French Pyrenean rivers. The presence of microplastics in these samples was confirmed by Raman microscopy and their morphology was defined by electron microscopy combined with energy-dispersive X-ray spectroscopy. The developed SP-ICP-MS method is suitable for the rapid screening of river waters for the presence of microplastics, which can then be analysed by inherently slower but more selective techniques (e.g., Raman microscopy).