Spontaneous Recycling of Electrosprayed Sample by Retrograde Motion of Microdroplets

Here, we discuss an interesting phenomenon occurring spontaneously near the sample liquid meniscus at the tip of the electrospray emitter. While most ejected droplets move from the emitter tip toward the counter electrode, some of the droplets decelerate and move backward to the liquid meniscus. When they hit the surface of the liquid meniscus, they either merge with the bulk liquid or get recharged during intermittent contact with the liquid meniscus and immediately reaccelerate toward the counter electrode. In some cases, while in contact with the meniscus they spontaneously form a secondary Taylor cone and emit progeny droplets. This observation suggests that the amount of electric charge transferred to such a droplet is sufficient to surpass the Rayleigh limit. Similar effects were previously observed for water as well as for NaCl-water and ethanol-water mixtures. However, here we observed it for electrolyte solutions commonly used in electrospray ionization mass spectrometry: methanol-water solutions with the addition of ammonium acetate, formic acid, or ammonium hydroxide. The reported phenomenon reveals the ongoing recycling of sample liquid in electrosprays. Such recycling can contribute to enhancement of sample utilization efficiency in electrospray ionization.