To investigate the stability of nanobubbles in natural hard water, a series of eight samples ranging in hardness from 0 to 332 mg/L CaCO3 were sonicated for periods of 5-45 min with an ultrasonic horn. Conductivity, temperature, zeta-potential, composition, and pH of the water were analyzed, together with the crystal structure of any calcium carbonate precipitate. Quasi-stable populations of bulk nanobubbles in Millipore and soft water are characterized by a zeta-potential of -35 to -20 mV, decaying over 60 h or more. After sonicating the hardest waters for about 10 min, they turn cloudy due to precipitation of amorphous calcium carbonate when the water temperature reaches 40 degrees C; the zeta-potential then jumps from -10 to +20 mV and remains positive for several days. From an analysis of the change of conductivity of the hard water before and after sonication, it is estimated that 37 +/- 5% of calcium was not originally in solution but existed in nanoscale prenucleation clusters, which decorate the nanobubbles formed in the early stages of sonication. Heating and charge screening in the nanobubble colloid cause the decorated bubbles to collapse or disperse, leaving an amorphous precursor of aragonite. Sonicating the soft supernatant increases its conductivity and pH and restores the negative zeta-potential associated with bulk nanobubbles, but there is no further precipitation. Our study of the correlation between nanobubble production and calcium agglomeration spanning the hardness and composition ranges of natural waters shows that the sonication method for introducing nanobubbles is viable only for hard water if it is kept cold; the stability of the nanobubble colloid will be reduced in any case by the presence of dissolved calcium and magnesium.
