Effect of inorganic ions on the ultrasound initiated degradation and product formation of triphenylmethane dyes

Triphenylmethane (TPM) dyes are an important category of dyes with a variety of industrial applications and consequently, these are found in the aquatic environment at relatively higher concentrations. Here, we report the degradation of two important TPM dyes (para rosaniline (PRA) and ethyl violet (EV)) in an aqueous medium by ultrasound which is one among the Advanced Oxidation Processes (AOPs). The main objective of this work is to study the effect of various inorganic ions on the degradation and the product formation of TPM dyes from the sonochemical reactions. Using a typical concentration of 10 ppm dyes and an ultrasonic frequency of 350 kHz and power of 60 W, a complete degradation of EV and PRA was observed with a pseudo first order rate constant of 0.2339 min−1 and 0.1956 min−1, respectively. The product analyses using high-resolution mass spectrometry (LC-Q-TOF-MS) revealed the formation of hydroxylated, de-alkylated, and other collapsed conjugated structure destructed products. The evolution of these products in the presence of various inorganic ions (Cl−, SO42−, NO3−, and CO3−) showed that only carbonate ions had a significant impact on the product evolution. The carbonate ions facilitated the formation of conjugated structure destructed product for both the dyes. This is attributed to the reactivity of carbonate radical, which facilitated the formation of carbon-centered radicals. This carbon-centered radical further undergoes reaction to cause the destruction of conjugated structures. This is confirmed by the identification of the corresponding product peaks in the mass spectra. The scavenging effect of carbonate ions was also reflected in the product study where there is a reduction in the formation of most of the hydroxylated products. One of the major inorganic species in any wastewater is carbonate ions and therefore the present result is very relevant to the understanding of oxidation based treatment protocol.